JP2010248346A - Polyol composition and polyurethane resin obtained using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition capable of obtaining a polyurethane resin extremely low in hardness, excellent in durability, and also having heat resistance, hydrolysis resistance and the like; and the polyurethane resin obtained using the polyol composition. <P>SOLUTION: In the polyol composition including a vinyl polymer (A) having a hydroxy group, an ester compound (B) and/or a carbonate compound (C), the vinyl polymer (A) has a hydroxyl value of 20 to 100 mgKOH/g, the ester compound (B) has a hydroxyl value of 0 mgKOH/g or larger and 60 mgKOH/g or smaller, and the carbonate compound (C) has a hydroxyl value of 0 mgKOH/g or larger and 60 mgKOH/g or smaller. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyol composition and a polyurethane resin obtained using the polyol composition. More specifically, the present invention relates to a polyol composition capable of obtaining a polyurethane resin having low hardness and excellent durability, and a polyurethane resin using the polyol composition.

  Conventionally, as a means for obtaining a polyurethane resin having low hardness from a polyol composition, generally, a plasticizer is often added to a raw material composition or the like. As the plasticizer, phthalates, non-aromatic dibasic esters, aliphatic esters, polyalkylene glycol esters, phosphate esters, trimellitic acid esters, chlorinated paraffins, Examples include hydrocarbon oils, process oils, polyethers, epoxidized plasticizers, and polyester plasticizers.

  Furthermore, many plasticizers are examined from the viewpoints of various uses using a polyurethane resin. For example, from a diester obtained by reacting polyethylene glycol having a molecular weight of 200 to 1000 with one or more fatty acids selected from the group consisting of saturated fatty acids having 6 to 10 carbon atoms, oleic acid and branched fatty acids having 8 to 18 carbon atoms. A plasticizer for polyurethane elastomers (see, for example, Patent Document 1). A low-acid-value monohydroxycarboxylic acid, which is a condensation polymer ester of a monohydroxycarboxylic acid having 18 to 20 carbon atoms, wherein the terminal carboxylic acid is substantially blocked with a hydrocarbon group or an alkoxy hydrocarbon group Acid condensation ester (for example, refer patent document 2). Reaction of a modified polyisocyanate that has an isocyanate group at the molecular end and is modified by a bond unit that does not contain a urethane bond and is derived from the reaction of an isocyanate group, and a monool as an active hydrogen component A plasticizer made of a urethane resin composition having an isocyanate group content of 0.5% or less, which is obtained by the treatment (see, for example, Patent Document 3). A plasticizer containing one or more esters of an aliphatic monocarboxylic acid having 12 to 24 carbon atoms and a monool having 1 to 10 carbon atoms and having a viscosity at 20 ° C. of 20 mPa · s or less (for example, , See Patent Document 4).

Further, as a means for adjusting the hardness of the polyurethane resin, in addition to adding a plasticizer, a polyol component which is a raw material of the urethane resin has been studied. For example, the polyol component is a polyether polyol having a polyoxyalkylene skeleton in which the repeating unit is represented by — (— O—CH ₃ —C (R) H —) — (see, for example, Patent Document 5). A composition containing a polycarbonate polyol obtained by reacting a raw material mixture containing a polyhydric alcohol having 5 or more carbon atoms and 3 or more valences, a monohydric alcohol having 5 or more carbon atoms and a carbonate compound (for example, patent document) 6).

Japanese Patent Laid-Open No. 7-173388 Japanese Patent Laid-Open No. 11-12224 JP 2000-234014 A JP 2002-356649 A JP 2003-342541 A JP 2006-299020 A

By containing a plasticizer as described above, a polyurethane resin molded product having a low hardness of, for example, 20 or less in C hardness can be obtained. However, from the obtained polyurethane resin molded product, the plasticizer may volatilize, resulting in thinning of the flesh or a decrease in flexibility. Moreover, durability, such as water resistance and hydrolysis resistance, may fall remarkably by addition of a plasticizer.
Further, even when the polyols described in Patent Documents 5 and 6 are used as raw materials for polyurethane resin, it is difficult to obtain a polyurethane resin having both low hardness of about 20 C hardness and durability. is there.

  The present invention solves the above-mentioned conventional problems, a polyol composition capable of obtaining a polyurethane resin having extremely low hardness, excellent durability, heat resistance and hydrolysis resistance, and the like It aims at providing the polyurethane resin using a polyol composition.

The present invention is as follows.
1. A polyol composition containing a vinyl polymer (A) having a hydroxyl group, an ester compound (B) and / or a carbonate compound (C),
The vinyl polymer (A) has a hydroxyl value of 20 to 100 mgKOH / g,
The ester compound (B) is obtained by reacting a hydrocarbon alcohol and a hydrocarbon carboxylic acid, and has a hydroxyl value larger than 0 mgKOH / g and 60 mgKOH / g or less,
The above-mentioned carbonate compound (C) is obtained by reacting a hydrocarbon alcohol and a carbonate compound, and has a hydroxyl value of more than 0 mgKOH / g and 60 mgKOH / g or less.
2. The number of hydroxyl groups contained in the vinyl polymer (A) is 3 or more. The polyol composition described in 1.
3. The number average molecular weight of the ester compound (B) and the carbonate compound (C) is 600 or more. Or 2. The polyol composition described in 1.
4). The molecular weight of the hydrocarbon alcohol and the hydrocarbon carboxylic acid is 100 or more. To 3. The polyol composition according to any one of the above.
5). At least one of the hydrocarbon alcohol and the hydrocarbon carboxylic acid has a branched structure. To 4. The polyol composition according to any one of the above.
6). The polyol composition has a hydroxyl value of 4 to 40 mg KOH / g. To 5. The polyol composition according to any one of the above.
7). The vinyl polymer (A) contains a structural unit derived from a (meth) acrylic acid hydroxyalkyl ester and a structural unit derived from a (meth) acrylic acid alkyl ester. To 6. The polyol composition according to any one of the above.
8). The content of the vinyl polymer (A) is 1 to 50% by mass when the total amount of the polyol composition is 100% by mass. To 7. The polyol composition according to any one of the above.
9. Above 1. To 8. A polyurethane resin obtained by using a raw material component comprising a polyol component containing the polyol composition according to any one of the above and a polyisocyanate component.

The polyol composition of the present invention is a polyol composition containing a vinyl polymer (A) having a hydroxyl group, an ester compound (B) and / or a carbonate compound (C), wherein the vinyl compound The polymer (A) has a hydroxyl value of 20 to 100 mgKOH / g, and the ester compound (B) is obtained by reacting a hydrocarbon alcohol and a hydrocarbon carboxylic acid, and has a hydroxyl value of 0 mgKOH / g. The carbonate compound (C) is obtained by reacting a hydrocarbon alcohol and a carbonate compound, and the hydroxyl value is greater than 0 mgKOH / g and not more than 60 mgKOH / g. Therefore, polyurethane resin having extremely low hardness, excellent durability, heat resistance, hydrolysis resistance, etc. It is suitable for elephants.
Moreover, in the polyol composition of this invention, when the number of the hydroxyl groups which a vinyl type polymer (A) has is three or more, it is suitable for manufacture of the polyurethane resin which balances low hardness and durability.
Moreover, when the number average molecular weights of the ester compound (B) and the carbonate compound (C) in the polyol composition of the present invention are 600 or more, production of a polyurethane resin having lower hardness and excellent heat resistance is achieved. It is suitable for.
Moreover, when the hydroxyl value of the polyol composition of the present invention is 4 to 40 mgKOH / g, a polyurethane resin having extremely low hardness, excellent durability, heat resistance, hydrolysis resistance and the like is easily produced. be able to.
The polyurethane resin of the present invention can be a polyurethane resin having extremely low hardness, excellent durability, and excellent heat resistance and hydrolysis resistance.

  The present invention will be described in detail below. In this specification, “(co) polymer” means a homopolymer and a copolymer, and “(meth) acryl” is used to mean one or both of acrylic and methacrylic.

[1] Polyol Composition The polyol composition of the present invention is a polyol composition containing a vinyl polymer (A) having a hydroxyl group, an ester compound (B) and / or a carbonate compound (C). The vinyl polymer (A) has a hydroxyl value of 20 to 100 mgKOH / g, and the ester compound (B) is obtained by reacting a hydrocarbon alcohol and a hydrocarbon carboxylic acid, And the hydroxyl value is greater than 0 mgKOH / g and not more than 60 mgKOH / g, and the carbonate compound (C) is obtained by reacting a hydrocarbon alcohol and a carbonate compound, and the hydroxyl value is greater than 0 mgKOH / g, 60 mg KOH / g or less.
In the present specification, the hydroxyl value (mgKOH / g) can be measured according to JIS K0070 (Testing method for hydroxyl value). That is, it refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid produced when a 1 g sample of the above component is reacted at a normal temperature and time using an acetylating agent based on a conventional method.

(1) Vinyl polymer (A)
The vinyl polymer (A) in the present invention is a (co) polymer obtained by polymerizing a vinyl monomer. This vinyl polymer (A) has a hydroxyl group, and the hydroxyl value is 20 to 100 mgKOH / g, preferably 20 to 60 mgKOH / g, and more preferably 20 to 55 mgKOH / g. When the hydroxyl value of the vinyl polymer (A) is within the above range, the polyurethane resin obtained from the polyol composition of the present invention has a low hardness, suppresses the occurrence of bleeding, and has excellent durability. Can be polyurethane resin

  The vinyl polymer (A) may be a polymer obtained from a hydroxyl group-containing vinyl monomer, or a copolymer obtained from a hydroxyl group-containing vinyl monomer and other vinyl monomers. it can. Preferably, it is a copolymer obtained from a hydroxyl group-containing vinyl monomer and other vinyl monomers. By polymerizing using a hydroxyl group-containing vinyl monomer, a vinyl polymer having a hydroxyl group can be efficiently produced.

Further, the number of hydroxyl groups (hereinafter also referred to as “number of hydroxyl groups”) of the vinyl polymer (A) is preferably 3 or more. Preferably it is 4 or more, more preferably 5 or more, and usually 20 or less.
When the number of hydroxyl groups is in the above range, the vinyl polymer (A) can sufficiently form a skeleton structure of a polyurethane resin, and can obtain a polyurethane having extremely low hardness and excellent durability.
The number of hydroxyl groups possessed by the vinyl polymer (A) can be calculated by a measuring instrument such as NMR.
Further, when the vinyl polymer (A) is a copolymer obtained by polymerizing a hydroxyl group-containing vinyl monomer and another vinyl monomer, the vinyl polymer (A) The number of hydroxyl groups possessed can also be calculated according to the following formula (1).
Number of hydroxyl groups (calculated number of hydroxyl groups) = number average molecular weight of vinyl polymer (A) / compounding (molar) ratio of raw material (vinyl monomer forming vinyl polymer (A)) and molecular weight Molecular weight per hydroxyl group (1)
The molecular weight per hydroxyl group (hereinafter also referred to as “calculated molecular weight”) calculated from the blending (molar) ratio and molecular weight of the raw material in the above formula (1) can be obtained from the following formula.
Calculated molecular weight = Molecular weight of hydroxyl group-containing vinyl monomer + [Molecular weight of other vinyl monomers × (Molecular amount of other vinyl monomers / Molecular amount of hydroxyl group-containing vinyl monomers) )]
For example, the vinyl polymer (A) having a number average molecular weight W is composed of a hydroxyl group-containing vinyl monomer (a) s mole, another vinyl monomer (b) t mole, and other vinyl monomers. When the molecular weights of (a), (b), and (c) are X, Y, and Z, respectively, the number of hydroxyl groups can be calculated from the following formula. can get.
Number of hydroxyl groups = W / [X + Y × (t mol / s mol) + Z × (u mol / s mol)]

  The number of hydroxyl groups in the vinyl polymer (A) of 3 or more means that the (co) polymer obtained from the vinyl monomer has an average of 3 or more hydroxyl groups. For example, in the case of a copolymer obtained from a hydroxyl group-containing vinyl monomer and other vinyl monomers, the obtained copolymer is a copolymer having an average of 3 or more hydroxyl groups.

By making the vinyl polymer (A) a polymer obtained from a hydroxyl group-containing vinyl monomer, or a copolymer obtained from a hydroxyl group-containing vinyl monomer and other vinyl monomers. The obtained copolymer has a hydroxyl group derived from the hydroxyl group-containing vinyl monomer used for the polymerization. Accordingly, the hydroxyl value of the vinyl polymer (A) is determined as desired from the blending ratio of the hydroxyl group-containing vinyl monomer and the hydroxyl group-containing vinyl monomer and the degree of polymerization (number average molecular weight) of the copolymer. You can choose.
Further, regarding the number of hydroxyl groups (average number of hydroxyl groups) obtained by the above calculation formula of the vinyl polymer (A), the blending ratio of the hydroxyl group-containing vinyl monomer and the hydroxyl group-containing vinyl monomer, and the copolymer The degree of polymerization (number average molecular weight) can be selected as desired.

  Hydroxyl group to be used when the vinyl polymer (A) is a compound obtained by polymerizing a hydroxyl group-containing vinyl monomer and another vinyl monomer polymerizable with the hydroxyl group-containing vinyl monomer. The blending ratio of the containing vinyl monomer and other vinyl monomers is not particularly limited. The ratio of the hydroxyl group-containing vinyl monomer to other vinyl monomers (hydroxyl group-containing vinyl monomer: other vinyl monomer) is (1: 3) to (1: 30) is preferred, (1: 4) to (1:25) are more preferred, and (1: 5) to (1:20) are even more preferred.

  The hydroxyl group-containing vinyl monomer is not particularly limited as long as it is a vinyl unsaturated compound having a hydroxyl group. From the viewpoint of physical properties (low hardness, durability, etc.) of the obtained polyurethane, (meth) acrylic acid is used. Hydroxyalkyl esters are preferred. Examples of the (meth) acrylic acid hydroxy ester include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 2- Examples include hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. These may be used alone or in combination of two or more.

  The other vinyl monomer is not particularly limited as long as it is a vinyl unsaturated compound polymerizable with the hydroxyl group-containing vinyl monomer. For example, (meth) acrylic acid alkyl ester compound, aromatic vinyl compound, ethylenically unsaturated carboxylic acid, acid anhydride, amino group-containing vinyl compound, amide group-containing vinyl compound, alkoxyl group-containing vinyl compound, cyano group-containing vinyl compound , Vinyl cyanide compounds, vinyl ether compounds, vinyl ester compounds, conjugated dienes and the like. These can be used alone or in combination of two or more. Among these, a (meth) acrylic acid alkyl ester monomer is preferable from the viewpoint of physical properties (low hardness, durability, etc.) of the obtained polyurethane.

  Examples of the (meth) acrylic acid alkyl ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (Meth) acrylic acid 2-methylpentyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-decyl, (meth) acrylic acid n-dodecyl, (meth) acrylic N-octadecyl acid, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Phenyl acrylate, and benzyl (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, Examples thereof include tert-butoxystyrene, vinyl toluene, vinyl naphthalene, halogenated styrene, styrene sulfonic acid and its salt, α-methyl styrene sulfonic acid and its salt, and the like. These may be used alone or in combination of two or more.

Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid. These may be used alone or in combination of two or more.
Examples of the acid anhydride monomer include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These may be used alone or in combination of two or more.

  Examples of the amino group-containing vinyl compound include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, and (meth) acrylic. 2- (di-n-propylamino) ethyl acid, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-n-propylamino) propyl (meth) acrylate , (Meth) acrylic acid 3-dimethylaminopropyl, (meth) acrylic acid 3-diethylaminopropyl, (meth) acrylic acid 3- (di-n-propylamino) propyl, and the like. These may be used alone or in combination of two or more.

  Examples of the amide group-containing vinyl compound include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide and the like. These may be used alone or in combination of two or more.

  Examples of the alkoxyl group-containing vinyl compound include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- ( n-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (n)-(meth) acrylate Butoxy) propyl and the like. These may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester compound having a cyano group include cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, ( 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 2-ethyl-6-cyano (meth) acrylate Examples include hexyl and 8-cyanooctyl (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. These may be used alone or in combination of two or more.

Examples of the vinyl ether compound include vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. These may be used alone or in combination of two or more.
Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, and vinyl propionate. These may be used alone or in combination of two or more.

  Conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5 -Diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like. These may be used alone or in combination of two or more.

  Other maleimide compounds such as maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; maleic acid ester compounds; itaconic acid ester compounds; N-vinyl heterocyclic compounds such as vinylpyridine Is mentioned. These may be used alone or in combination of two or more.

  When the vinyl polymer (A) is a copolymer composed of a structural unit derived from a hydroxyl group-containing vinyl monomer and a structural unit derived from another vinyl monomer, The mass ratio of the hydroxyl group-containing vinyl monomer unit constituting A) to other vinyl monomer units (hydroxyl group-containing vinyl monomer: other vinyl monomer) is (1: 3). ) To (1:30) are preferred, (1: 4) to (1:25) are more preferred, and (1: 5) to (1:20) are more preferred. When the mass ratio is within the above range, the vinyl polymer (A) is preferable because it can sufficiently have a hydroxyl group.

The vinyl polymer (A) is preferably a copolymer having a structural unit derived from a (meth) acrylic acid hydroxyalkyl ester and a structural unit derived from a (meth) acrylic acid alkyl ester. In this case, the vinyl polymer (A) may contain the structural unit derived from the hydroxyalkyl ester of (meth) acrylic acid and the structural unit derived from the alkyl ester of (meth) acrylic acid as a whole, and is contained in part. May be. When the vinyl polymer (A) is a copolymer partially containing a structural unit derived from a (meth) acrylic acid hydroxyalkyl ester and a structural unit derived from a (meth) acrylic acid alkyl ester, the other structure As a unit, the structural unit derived from the above-mentioned vinyl-type monomer is mentioned.

In the vinyl polymer (A), the content of the structural unit derived from the (meth) acrylic acid hydroxyalkyl ester and the structural unit derived from the (meth) acrylic acid alkyl ester is the total content of the vinyl polymer (A). When it is 100 mass%, 50-100 mass% is preferable, 70-100 mass% is more preferable, 90-100 mass% is still more preferable.
Moreover, the mass ratio of the structural unit derived from the (meth) acrylic acid hydroxyalkyl ester and the structural unit derived from the (meth) acrylic acid alkyl ester (the structural unit derived from the (meth) acrylic acid hydroxyalkyl ester: alkyl (meth) acrylate The structural unit derived from the ester is preferably (1: 3) to (1:30), more preferably (1: 4) to (1:25), and further (1: 5) to (1:20). preferable. When the mass ratio is within the above range, the vinyl polymer (A) is preferable because it can sufficiently have a hydroxyl group.

  The number average molecular weight of the vinyl polymer (A) is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 3,000 to 10,000. 000. When the number average molecular weight is within the above range, the viscosity is low and the workability is excellent, and the polyurethane resin obtained from the polyol composition containing the vinyl polymer (A) is excellent in flexibility.

The viscosity at 25 ° C. of the vinyl polymer (A) is not particularly limited, but is preferably 1,000,000 mPa · s or less, more preferably 500,000 mPa · s or less, and still more preferably 300,000 mPa · s. It is below (usually 10,000 mPa · s or more, preferably 50,000 mPa · s or more). When the viscosity is within the above range, for example, it is preferable because it is easy to handle in the production of polyurethane resin and the like.
The viscosity of the vinyl polymer (A) can be measured by, for example, a B-type viscometer.

The manufacturing method of a vinyl polymer (A) is not specifically limited, The normal polymerization method of a vinyl monomer can be used. Specifically, it can be produced by polymerizing a hydroxyl group-containing vinyl monomer and other vinyl monomers in the presence of a radical polymerization initiator. Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
In addition, the hydroxyl group-containing vinyl monomer and other vinyl monomers used in the production of the vinyl polymer (A) and the blending ratio thereof are as described above.

  Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide (BPO), ditertiary butyl peroxide, lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate; 2,2 ′ -Azobispropane, 2,2'-dichloro-2,2'-azobispropane, 2,2'-azobisisobutane, 2,2'-azobisisobutylamine, 2,2'-azobisisobutyro Nitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, azobisisovaleronitrile, etc. Azo compounds; persulfates such as sodium persulfate, ammonium persulfate and potassium persulfateThese can be used alone or in combination of two or more. Moreover, although the usage-amount of the said radical polymerization initiator changes with kinds, superposition | polymerization conditions, etc. with respect to the whole quantity of a hydroxyl-containing vinyl monomer and other vinyl monomers, it is 0.001-1. 5% by mass.

  In the polymerization, it is preferable to use a polymerization solvent. Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents can be used alone or in combination of two or more. The amount of the polymerization solvent used is usually 50 to 1000 parts by weight with respect to the total amount of the hydroxyl group-containing vinyl monomer and other vinyl monomers, although it varies depending on the type and polymerization conditions.

  In the polymerization, a chain transfer agent can also be used. Examples of the chain transfer agent include ethanethiol, butanethiol, dodecanethiol, benzenethiol, toluenethiol, α-toluenethiol, phenethyl mercaptan, 2-mercaptoethanol, 3-mercaptopropanol, n-hexyl mercaptan, and n-octyl mercaptan. , N-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, thioglycolic acid-containing compounds such as thioglycolic acid. These can be used alone or in combination of two or more. The amount of the chain transfer agent used varies depending on the type, polymerization conditions, etc., but is usually 0.001 to 1.0% by mass with respect to the total amount of the hydroxyl group-containing vinyl monomer and other vinyl monomers. It is.

In the production of the vinyl polymer (A), the hydroxyl group-containing vinyl monomer and other vinyl monomers, the polymerization solvent, the polymerization initiator, etc. are charged all at once into the reaction vessel to initiate the polymerization. Alternatively, they may be added continuously or intermittently when the reaction is continued. This polymerization is usually preferably performed at a polymerization temperature of 0 to 150 ° C., preferably 0 to 100 ° C., using a reactor from which oxygen has been removed. During the reaction, the raw material addition method, temperature, production conditions such as stirring, etc. can be appropriately changed. The polymerization method may be a continuous method or a batch method.
The polymerization time is usually about 0.01 to 30 hours. Further, when the predetermined polymerization conversion rate is reached, the polymerization can be stopped by adding a polymerization terminator or the like. As the polymerization terminator, amine compounds such as hydroxylamine and N, N-diethylhydroxylamine, quinone compounds such as hydroquinone, and the like are used.

(2) Ester compound (B)
The ester compound (B) is an ester compound obtained by reacting a raw material containing a hydrocarbon alcohol and a hydrocarbon carboxylic acid, and having a hydroxyl value of greater than 0 mgKOH / g and 60 mgKOH / g or less.

  The hydroxyl value of the ester compound (B) is greater than 0 mgKOH / g and 60 mgKOH / g or less, preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g. When the hydroxyl value of the ester compound (B) is in the above range, the polyurethane resin obtained by using the polyol composition containing the ester compound (B) has low hardness and bleed. Generation | occurrence | production is suppressed and it can be set as the polyurethane resin excellent in durability. That is, if the hydroxyl value is 0, bleeding may occur in the obtained polyurethane resin. On the other hand, when the hydroxyl value exceeds 60 mgKOH / g, the hardness value of the resulting polyurethane resin may increase.

  The hydrocarbon alcohol is not particularly limited, and is a hydrocarbon monohydric alcohol (hereinafter simply referred to as “monohydric alcohol”), a hydrocarbon dihydric alcohol (hereinafter simply referred to as “dihydric alcohol”), Also, a hydrocarbon-based polyhydric alcohol (hereinafter simply referred to as “polyhydric alcohol”) can be used. The hydrocarbon alcohol is preferably a hydrocarbon dihydric alcohol or a hydrocarbon alcohol containing a hydrocarbon polyhydric alcohol, more preferably a hydrocarbon alcohol comprising a dihydric alcohol and / or a polyhydric alcohol. It is alcohol. By using a dihydric alcohol or a polyhydric alcohol as the hydrocarbon alcohol, the resulting ester compound can have a hydroxyl group derived from the hydrocarbon alcohol, whereby the ester compound has a predetermined hydroxyl group. A value can be obtained.

  Further, since the ester compound (B) has a hydroxyl value larger than 0 mgKOH / g and not more than 60 mgKOH / g and has a hydroxyl group, the polyol composition of the present invention containing the ester compound (B) is used. When a polyurethane resin is produced, the ester compound (B) forms an urethane bond with an isocyanate and is incorporated into the urethane skeleton of the polyurethane resin. Thereby, the ester compound (B) has a function of reducing the hardness of the polyurethane, which is equal to or higher than that of a commonly used plasticizer, and the ester compound (B) does not ooze out of the polyurethane resin, Bleeding is suppressed.

  The hydrocarbon-based carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids or polycarboxylic acids having one or more carboxyl groups in one molecule, and oxycarboxylic acids having a carboxyl group and a hydroxyl group in one molecule. Can be mentioned. When monohydric alcohol is used in the alcohol, it is preferable to use oxycarboxylic acid for the hydrocarbon carboxylic acid. By using oxycarboxylic acid, a hydroxyl group derived from the oxycarboxylic acid can be provided. On the other hand, when a dihydric alcohol and / or a polyhydric alcohol is used, a monocarboxylic acid having no hydroxyl group may be used.

  In this invention, the ester compound (B) obtained by using a bihydric alcohol or a polyhydric alcohol can be equipped with the hydroxyl group derived from the said bihydric alcohol or a polyhydric alcohol. Moreover, the ester compound (B) obtained by using oxycarboxylic acid can be equipped with the hydroxyl group derived from the said oxycarboxylic acid. That is, in the present invention, an ester compound (B) having a predetermined hydroxyl value can be obtained by appropriately selecting and using a dihydric alcohol, a polyhydric alcohol, or oxycarboxylic acid.

  Moreover, when using a dihydric alcohol or a polyhydric alcohol, or oxycarboxylic acid, it is not necessary for all of the formed ester compound (B) to have a hydroxyl group. It is sufficient that a part of the ester compound obtained by the esterification reaction has a hydroxyl group. As a result, the hydroxyl value of the ester compound (B) obtained by the esterification reaction from alcohol and carboxylic acid is 0 mgKOH / It may be larger than g and 60 mgKOH / g or less.

The number of hydroxyl groups (number of hydroxyl groups) in the ester compound (B) is preferably larger than 0 and smaller than 2. More preferably, it is 0.2-1.8, More preferably, it is 0.3-1. When the number of hydroxyl groups is in the above range, it is possible to obtain a polyurethane resin that has low hardness, suppresses bleeding, and has excellent durability.
The number of hydroxyl groups possessed by the ester compound (B) can be calculated in the same manner as a measuring instrument such as NMR or the above formula (1).
The number of hydroxyl groups of the ester compound (B) can be specifically calculated from the following formula (2).
Number of hydroxyl groups (number of calculated hydroxyl groups) = number average molecular weight of ester compound (B) / mixture (mole) ratio of raw material (compound forming ester compound (B)) and molecular weight calculated per molecular weight ... (2)
The molecular weight per hydroxyl group (hereinafter also referred to as “calculated molecular weight”) calculated from the blending (molar) ratio and molecular weight of the raw material in the above formula (2) can be obtained from the following formula.
Calculated molecular weight = molecular weight of compound (a) provided with hydroxyl group in ester compound (B) + [molecular weight of other compound (b) other than compound (a) × (each compounding molar amount of other compound (b)) / Molecular amount of compound (a))]
The number of hydroxyl groups in the ester compound (B) means the average number of hydroxyl groups of the ester compound obtained by reacting a raw material containing a hydrocarbon alcohol and a hydrocarbon carboxylic acid.

  Furthermore, it is preferable that at least one of alcohol and carboxylic acid is a compound having a branched structure. When at least one of the alcohol and carboxylic acid is an alcohol or carboxylic acid having a branched structure, the viscosity of the resulting ester compound can be lowered, and the resulting polyurethane resin can be a low-hardness polyurethane resin. .

  As the polyhydric alcohol, (1) a polyhydric alcohol having 3 or more, particularly 3 to 6 methylol groups, and having 1 to 5 carbon atoms excluding the methylol groups (trimethylolethane, trimethylol) Polytrimethylolpropane such as propane, trimethyloloctane and ditrimethylolpropane, polypentaerythritol such as pentaerythritol and dipentaerythritol, and polyhydric alcohols having a cyclic structure such as tetramethylolcyclohexane), (2) diglycerin and the like Examples include polyglycerin, (3) 2,2,6,6-tetrakis (hydroxymethyl) cyclohexyl alcohol, sorbitol, and sucrose. This polyhydric alcohol is polyether polyol, polyester polyol, polytetramethylene ether glycol, tetrahydrofuran-alkylene oxide copolymer polyol, epoxy-modified polyol, hydrocarbon polyol, acrylic polyol, ethylene-vinyl acetate copolymer part. Even if it has a structural part consisting of general-purpose or special polyols such as saponified products, flame retardant polyols, xylene skeleton polyols, vegetable oil modified polyols such as castor oil-based polyols, silicon-containing polyols, fluorine-containing polyols and nitrogen-containing polyols Good. As this polyhydric alcohol, trimethylolpropane, pentaerythritol and the like are preferable. These can be used alone or in combination of two or more. Further, only polyhydric alcohols having the same valence may be used, or polyhydric alcohols having different valences may be used in combination.

  The dihydric alcohol preferably has 5 or more carbon atoms, more preferably 6 or more, and still more preferably 6 to 36. The structure of the hydrocarbon skeleton of the dihydric alcohol is not particularly limited, and the hydrocarbon skeleton may have a linear structure or a branched structure. When it has a branched structure, the resulting polyol composition is preferred because it has lower crystallinity and lower viscosity. Further, the hydrocarbon skeleton may have a cyclic structure, and the cyclic skeleton may have only a saturated bond or may have an unsaturated bond.

  Examples of the dihydric alcohol include (1) polyalkylene glycol (triethylene glycol, dipropylene glycol, tripropylene glycol, etc.), and (2) linear alkylene glycol having 5 to 36 carbon atoms (pentanediol, hexanediol, octanediol). And (3) dihydric alcohols having a branched structure (3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, diethylpentanediol, trimethylhexanediol and neo Pentyl glycol and the like), (4) dihydric alcohols having a cyclic structure (1,4-cyclohexanedimethanol and the like), (5) dimer diol, hydrogenated dimer diol and the like. The dihydric alcohol is a polyether polyol, polyester polyol, polytetramethylene ether glycol, tetrahydrofuran-alkylene oxide copolymer polyol, epoxy-modified polyol, hydrocarbon polyol, acrylic polyol, ethylene-vinyl acetate copolymer part. Even if it has a structural part consisting of general-purpose or special polyols such as saponified products, flame retardant polyols, xylene skeleton polyols, vegetable oil modified polyols such as castor oil-based polyols, silicon-containing polyols, fluorine-containing polyols and nitrogen-containing polyols Good. These can be used alone or in combination of two or more.

  The monohydric alcohol preferably has 5 or more carbon atoms, more preferably 6 or more, and still more preferably 8 to 36. The structure of the hydrocarbon skeleton of the monohydric alcohol is not particularly limited, and the hydrocarbon skeleton may have a linear structure or a branched structure. When it has a branched structure, the resulting polyol composition is preferred because of its lower viscosity and lower crystallinity. Moreover, the hydrocarbon skeleton may have a cyclic structure, and this cyclic structure may have only a saturated bond or may have an unsaturated bond. As this monohydric alcohol, an alkyl alcohol is preferable, and an alkyl alcohol having a branched structure is more preferable.

  Examples of the monohydric alcohol include (1) monohydric alcohols having a linear alkyl group (hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, stearyl alcohol, etc.), (2 ) Monohydric alcohols having a cyclic structure (such as cyclohexyl alcohol and 4-tert-butylcyclohexyl alcohol), (3) monohydric alcohols having a branched structure (2-ethylhexyl alcohol, isohexyl alcohol, isononyl alcohol, isodecyl alcohol, Isotridecyl alcohol, isohexadecyl alcohol and isostearyl alcohol), (4) glycol ethers (ethylene glycol monobutyl ether, diethylene glycol) Monobutyl ether) and the like. The monohydric alcohol is preferably an alkyl alcohol having a branched structure such as 2-ethylhexyl alcohol, isotridecyl alcohol, and isohexadecyl alcohol. These can be used alone or in combination of two or more.

  Examples of the monocarboxylic acid or polycarboxylic acid include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, montanic acid, oleic acid, linoleic acid, linolenic acid, and the like. Fatty acids such as coconut oil fatty acid, palm oil fatty acid, olive oil fatty acid, beef tallow fatty acid, hydrogenated beef tallow fatty acid, and synthetic fatty acids containing these. In addition, lower or intermediate fatty acids such as butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, dibasic acids such as anhydrides, adipic acid, azelaic acid, sebacic acid, hydrogenated dimer acid, etc. And polybasic acids such as acid anhydride and trimellitic acid, and anhydrides thereof. These can be used alone or in combination of two or more.

  Examples of the oxycarboxylic acid include castor oil fatty acid (main component: ricinoleic acid), hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid), 11- or 16-hydroxyhexadecanoic acid, 16-hydroxyhexadecenoic acid, 2 -Or 18-hydroxy octadecanoic acid, 22-hydroxy docosanoic acid, 2-hydroxy tetracosanoic acid, dihydroxy myristic acid, dihydroxy palmitic acid, dihydroxy stearic acid, dihydroxy arachidic acid, trihydroxy palmitic acid, from lesclella oil (Lesquerella Oil) Obtained Rescrelic acid acid, Demorphecolic acid obtained from Demorphotheca Oil (Demorphecolic Acid) Epoxidized unsaturated oils (epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized tall oil, etc.) is a hydroxyl carboxylic acid such as ring-opened after a fatty acid to decompose. The higher oxycarboxylic acid exemplified above may be used in the form of an ester such as a lower alkyl ester. These can be used alone or in combination of two or more.

When polyhydric alcohol and monohydric alcohol are used, the mass ratio of polyhydric alcohol and monohydric alcohol is not particularly limited, but when the total of polyhydric alcohol and monohydric alcohol is 100% by mass, polyhydric alcohol Is preferably 20 to 95% by mass, more preferably 30 to 85% by mass. A mass ratio of the polyhydric alcohol of 20 to 95% by mass is preferable because a polyurethane resin having good physical properties with suppressed bleeding can be obtained.
The combination of the polyhydric alcohol and the monohydric alcohol is not particularly limited. For example, the number of carbon atoms in the portion having 3 or more, particularly 3 to 5 methylol groups, and excluding the methylol group is 2 to 8. A combination of a polyhydric alcohol and a monohydric alcohol having a branched structure is preferred.

In the case of using a dihydric alcohol and a monohydric alcohol, the mass ratio of the dihydric alcohol and the monohydric alcohol is not particularly limited, but when the total of the dihydric alcohol and the monohydric alcohol is 100% by mass, the dihydric alcohol is used. Is preferably 20 to 95% by mass, more preferably 30 to 85% by mass. A mass ratio of the dihydric alcohol of 20 to 95% by mass is preferable because a polyurethane resin having good physical properties with suppressed bleeding can be obtained.
Although the combination of a dihydric alcohol and a monohydric alcohol is not specifically limited, For example, the combination of the C6-C36 dihydric alcohol and the monohydric alcohol which has a branched structure is preferable.

Further, when polyhydric alcohols, dihydric alcohols and monohydric alcohols are used, the mass ratio (polyhydric alcohol: dihydric alcohol: monohydric alcohol) is when the total mass of the hydrocarbon-based alcohol is 100 mass%. (0-95) :( 0-95) :( 5-80) is preferable, and (0-85) :( 0-85) :( 15-70) is more preferable. When the mass ratio of the hydrocarbon-based alcohol is within the above range, it is preferable because a polyurethane resin having excellent physical properties with extremely low hardness and suppressed bleeding can be obtained.
In the case of using a polyhydric alcohol, a dihydric alcohol and a monohydric alcohol, the combination is not particularly limited. For example, the above-described portion having 3 or more, particularly 3 to 6 methylol groups and excluding the methylol group A combination of a polyhydric alcohol having 2 to 8 carbon atoms, a dihydric alcohol having the above branched structure, and a monohydric alcohol having the above branched structure is preferable.

  The blending ratio of the hydrocarbon-based alcohol and the hydrocarbon-based carboxylic acid is not particularly limited, but preferably (1: 1) to (3: 1) is preferable in terms of molar ratio (alcohol: carboxylic acid), (1: 1) to (5: 1). In the esterification reaction, when the alcohol is distilled out of the system, it is preferable to charge the alcohol in excess.

  The number average molecular weight of the ester compound (B) is not particularly limited, but is preferably 100 to 10,000, more preferably 300 to 5,000, and still more preferably 1,000 to 2,000. . When the number average molecular weight is within the above range, the obtained polyurethane resin can be a polyurethane resin having low hardness and excellent durability.

The viscosity at 25 ° C. of the ester compound (B) is not particularly limited, but can be 5000 mPa · s or less, 15000 mPa · s or less, particularly 1000 mPa · s or less, and further 500 mPa · s or less (usually 50 Pa · s). Or more). When this viscosity is in the above range, the obtained polyurethane resin can be made into a low-hardness polyurethane resin, and it is preferable because it is easy to handle in the production of polyurethane resins.
The viscosity of this polycarbonate polyol composition can be measured by, for example, a B-type viscometer.

  In the ester compound (B), at least one of the hydrocarbon alcohol and the hydrocarbon carboxylic acid used preferably has a molecular weight of 100 or more, more preferably 200 or more, and still more preferably 300 or more. By using a compound in the above range, the number average molecular weight of the ester compound (B) can be easily set to 100 or more.

Preferred embodiments (combinations) of the hydrocarbon alcohol and hydrocarbon carboxylic acid for forming the ester compound (B) are as follows.
(1) A hydrocarbon dihydric alcohol having a molecular weight of 200 to 900 (more preferably 300 to 800) and a hydrocarbon monocarboxylic acid having a molecular weight of 100 to 400 (more preferably 120 to 350) and having a branched structure.
(2) a hydrocarbon dihydric alcohol having a molecular weight of 300 or less (further 200 or less, particularly 100 or less), a hydrocarbon monocarboxylic acid having a molecular weight of 200 to 400 (more preferably 250 to 350), And a hydrocarbon monocarboxylic acid having a molecular weight of 200 to 400 (more preferably 250 to 350) and a branched structure.
(3) a hydrocarbon trihydric alcohol having a molecular weight of 300 or less (further 200 or less, particularly 150 or less), a hydrocarbon monocarboxylic acid having a molecular weight of 200 to 400 (more preferably 250 to 350), And a hydrocarbon monocarboxylic acid having a molecular weight of 200 to 400 (more preferably 250 to 350) and a branched structure.

  About the aspect of said (1), specifically, hydrogenated dimer diol obtained by complete hydrogenation of dimer acid, 1,12 hydroxystearyl alcohol, and castor oil fatty acid were reduced as hydrocarbon type dihydric alcohol. Castor alcohol and the like. Examples of the carboxylic acid include 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, isododecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachic acid and the like.

  In the embodiment (2), specifically, the hydrocarbon dihydric alcohol includes 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1, Examples include 3-hexanediol, 1,6 hexanediol, and 1,4 butanediol. Examples of the hydrocarbon monocarboxylic acid include castor oil fatty acid and hydrogenated castor oil fatty acid. Examples of the hydrocarbon monocarboxylic acid having a branched structure include 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, isododecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, and isoarachidic acid.

  About the aspect of said (3), a trimethylol propane, a trimethylol ethane, a trimethylol octane etc. are specifically mentioned as a hydrocarbon type trihydric alcohol. Examples of the hydrocarbon monocarboxylic acid include castor oil fatty acid and hydrogenated castor oil fatty acid. Examples of the hydrocarbon monocarboxylic acid having a branched structure include 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, isododecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, and isoarachidic acid.

The production method of the ester compound (B) is not particularly limited and can be obtained by reacting a hydrocarbon alcohol and a hydrocarbon carboxylic acid. That is, it can be produced by esterifying a hydrocarbon alcohol and a hydrocarbon carboxylic acid.
In the production of the ester compound (B), the hydrocarbon alcohol and hydrocarbon carboxylic acid used and the blending ratio thereof are as described above.

  The production conditions and reaction conditions for producing the ester compound (B) are not particularly limited, and general ester production methods can be used. For example, it can be as follows.

  When reacting a hydrocarbon-based alcohol and a hydrocarbon-based carboxylic acid, a catalyst generally used in an esterification reaction of an alcohol and a carboxylic acid can be used. The catalyst is preferably a strong acid catalyst, and examples thereof include sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, boron trifluoride ethylate, and tin tetrachloride. These can be used alone or in combination of two or more.

  Moreover, although the usage-amount of the said catalyst changes with manufacturing conditions etc., 5-2000 ppm is preferable with respect to the sum total of hydrocarbon type alcohol and hydrocarbon type carboxylic acid, 10-800 ppm, Furthermore, 20-600 ppm. It is preferable that When the usage-amount of an esterification reaction catalyst exists in the said range, transesterification progresses appropriately.

The esterification reaction proceeds even without a solvent, but a solvent can also be used. The solvent used for the esterification reaction is not particularly limited as long as it is a non-polar solvent or a polar solvent as long as it is an inert solvent for the esterification reaction. For example, alkanes such as hexane, heptane, and octane; haloalkanes such as methylene chloride, chloroform, carbon tetrachloride, and ethylene chloride; benzenes such as benzene, toluene, xylene, mesitylene, and pentamethylbenzene; chlorobenzene, bromobenzene, and the like Halobenzenes; ethers such as diethyl ether and anisole;
Moreover, although the usage-amount in the case of using the said solvent changes with ester manufacturing conditions etc., it is 50-1000 mass parts normally with respect to 100 mass parts of hydrocarbon type alcohol and hydrocarbon type carboxylic acid.

  The reaction conditions for the esterification reaction are not particularly limited. For example, the temperature of the reactor into which the raw material mixture has been charged is distilled out of the system from the room temperature (for example, 20 to 30 ° C.) under normal pressure (for example, 0.098 MPa). However, the temperature is gradually raised to a predetermined temperature of 100 to 280 ° C., particularly 140 to 260 ° C., and further 160 to 240 ° C. over 8 to 24 hours, particularly 12 to 20 hours. Then, the predetermined temperature is maintained until the water produced by the reaction is no longer distilled, and the reaction is continued. Thereafter, while maintaining the predetermined temperature, the pressure in the reactor is gradually reduced to 1 to 100 kPa, particularly 1 to 50 kPa, further 1 to 10 kPa for 2 to 8 hours, particularly 4 to 6 hours, and further 1 to 20 hours. In particular, the reaction can be carried out for 2 to 15 hours.

  Furthermore, the ester compound (B) is prepared by adjusting the mass ratio of the hydrocarbon alcohol and the hydrocarbon carboxylic acid, the type and amount of the esterification reaction catalyst, the reaction conditions for the esterification reaction, and the like. It can also have the desired structure and physical properties.

In the esterification reaction, a by-product such as water produced as a by-product must be continuously and efficiently distilled out of the system. Therefore, it is preferable to distill off by-products such as water produced as a by-product at a predetermined temperature in the temperature raising step from room temperature and normal pressure and the subsequent reaction. Furthermore, in the reaction under reduced pressure, the inside of the reactor can be reduced from normal pressure to the above pressure at a predetermined temperature, whereby distillation of byproducts such as by-product water can be promoted. Thus, in order to distill off by-products such as by-product water out of the system, the reactor is preferably provided with a distillation column or the like.
Moreover, it is preferable to circulate inert gas, such as nitrogen gas and argon, in a reactor on said reaction conditions, and to accelerate | stimulate distillation of by-products, such as by-product water.

(3) Carbonate compound (C)
The carbonate compound (C) is a carbonate compound (C) obtained by reacting a raw material mixture containing a hydrocarbon alcohol and a carbonate compound, and having a hydroxyl value of greater than 0 mgKOH / g and not more than 60 mgKOH / g. .

  The hydroxyl value of the carbonate compound (C) is larger than 0 mgKOH / g and not more than 60 mgKOH / g, preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g. When the hydroxyl value of the carbonate compound (C) is in the above range, the polyurethane resin obtained by using the polyol composition containing the carbonate compound (C) has low hardness and bleed. Generation | occurrence | production is suppressed and it can be set as the polyurethane resin excellent in durability. That is, if the hydroxyl value is 0, bleeding may occur in the obtained polyurethane resin. On the other hand, when the hydroxyl value exceeds 60 mgKOH / g, the hardness value of the resulting polyurethane resin may increase.

  In addition, since the carbonate compound (C) has a hydroxyl value larger than 0 mgKOH / g and 60 mgKOH / g or less and has a hydroxyl group, the polyol composition of the present invention containing the carbonate compound (C) is used. When a polyurethane resin is produced, the carbonate compound (C) forms an urethane bond with an isocyanate and is incorporated into the urethane skeleton of the polyurethane resin. Thereby, the carbonate-based compound (C) has a function of reducing the hardness of the polyurethane, which is equal to or higher than that of a commonly used plasticizer, and the carbonate-based compound (C) does not ooze out from the polyurethane resin. Bleeding is suppressed.

  The hydrocarbon alcohol is not particularly limited, and monohydric alcohols, dihydric alcohols, and polyhydric alcohols can be used. The hydrocarbon alcohol is preferably a dihydric alcohol or a hydrocarbon alcohol containing a polyhydric alcohol, more preferably a dihydric alcohol and / or a polyhydric alcohol. By using a dihydric alcohol or a polyhydric alcohol as the hydrocarbon-based alcohol, the resulting carbonate-based compound (C) has a hydroxyl group derived from the alcohol and can sufficiently ensure the value of the hydroxyl value. . Furthermore, it is preferable to use a dihydric alcohol or a polyhydric alcohol because the molecular weight of the carbonate compound (C) can be increased.

  Moreover, when using a hydrocarbon type dihydric alcohol or a hydrocarbon type polyhydric alcohol as a hydrocarbon type alcohol, all of the carbonate type compounds (C) formed do not need to have a hydroxyl group. It is sufficient that a part of the ester compound obtained by the esterification reaction has a hydroxyl group. As a result, the hydroxyl value of the ester compound (B) obtained by the esterification reaction from alcohol and carboxylic acid is 0 mgKOH / It may be larger than g and 60 mgKOH / g or less.

Further, the number of hydroxyl groups (number of hydroxyl groups) of the carbonate compound (C) is preferably larger than 0 and smaller than 2. More preferably, it is 0.2-1.8, More preferably, it is 0.3-1. When the number of hydroxyl groups is in the above range, it is possible to obtain a polyurethane resin that has low hardness, suppresses bleeding, and has excellent durability.
The number of hydroxyl groups possessed by the carbonate compound (C) can be calculated in the same manner as a measuring instrument such as NMR or the above formula (1).
The number of hydroxyl groups of the carbonate compound (C) can be specifically calculated from the following formula (3).
Number of hydroxyl groups (calculated number of hydroxyl groups) = number average molecular weight of carbonate compound (C) / mixture (mole) ratio of raw material (compound forming carbonate compound (C)) and molecular weight calculated per molecular weight ... (3)
The molecular weight per hydroxyl group (hereinafter also referred to as “calculated molecular weight”) calculated from the blending (molar) ratio and molecular weight of the raw material in the above formula (3) can be obtained from the following formula.
Calculated molecular weight = molecular weight of the compound (a) provided with a hydroxyl group in the carbonate-based compound (C) + [each molecular weight of the other compound (b) other than the compound (a) × (each compounding molar amount of the other compound (b)) / Molecular amount of compound (a))]
In addition, the said hydroxyl group number of carbonate type compound (C) means the average number of the hydroxyl groups which a carbonate type compound has obtained by making the raw material containing a hydrocarbon type alcohol and a carbonate compound react.

  For the polyhydric alcohol, dihydric alcohol and monohydric alcohol used for forming the carbonate compound (C), the description of the polyhydric alcohol, dihydric alcohol and monohydric alcohol in the ester compound (B) is applied as it is. it can. The alcohol preferably includes an alcohol having a branched structure. When the alcohol has a branched structure, the value of the viscosity of the obtained carbonate compound can be lowered, and the obtained polyurethane resin can be a low-hardness polyurethane resin.

  Although it does not specifically limit as said carbonate compound, From a synthetic viewpoint, 300 or less are preferable for molecular weight, More preferably, the low molecular carbonate compound of 250 is preferable. Examples of the carbonate compound include dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl isobutyl carbonate. Examples of the diaryl carbonate include diphenyl carbonate and dibenzyl carbonate. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,2-pentylene carbonate, and the like. Among these, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, ethylene carbonate, and the like can be given. This carbonate compound may be used alone or in combination of two or more.

When polyhydric alcohol and monohydric alcohol are used as the hydrocarbon alcohol, the mass ratio of polyhydric alcohol and monohydric alcohol is not particularly limited, but the total of polyhydric alcohol and monohydric alcohol is 100% by mass. In this case, the polyhydric alcohol is preferably 20 to 95% by mass, particularly preferably 30 to 85% by mass. A mass ratio of the polyhydric alcohol of 20 to 95% by mass is preferable because a polyurethane resin having good physical properties with suppressed bleeding can be obtained.
The combination of the polyhydric alcohol and the monohydric alcohol is not particularly limited. For example, the number of carbon atoms in the portion having 3 or more, particularly 3 to 5 methylol groups, and excluding the methylol group is 1 to 8. A combination of a polyhydric alcohol and a monohydric alcohol having a branched structure is preferred.

In the case of using a dihydric alcohol and a monohydric alcohol, the mass ratio of the dihydric alcohol and the monohydric alcohol is not particularly limited, but when the total of the dihydric alcohol and the monohydric alcohol is 100% by mass, the dihydric alcohol is used. Is preferably 20 to 95% by mass, more preferably 30 to 85% by mass. A mass ratio of the dihydric alcohol of 20 to 95% by mass is preferable because a polyurethane resin having good physical properties with suppressed bleeding can be obtained.
Although the combination of a dihydric alcohol and a monohydric alcohol is not specifically limited, For example, the combination of the C6-C36 dihydric alcohol and the monohydric alcohol which has a branched structure is preferable.

Further, when polyhydric alcohols, dihydric alcohols and monohydric alcohols are used, the mass ratio (polyhydric alcohol: dihydric alcohol: monohydric alcohol) is when the total mass of the hydrocarbon-based alcohol is 100 mass%. (0-95) :( 0-95) :( 5-80) is preferable, and (0-85) :( 0-85) :( 15-70) is more preferable. When the mass ratio of the hydrocarbon-based alcohol is within the above range, it is preferable because a polyurethane resin having excellent physical properties with extremely low hardness and suppressed bleeding can be obtained.
In the case of using a polyhydric alcohol, a dihydric alcohol and a monohydric alcohol, the combination is not particularly limited. For example, the above-described portion having 3 or more, particularly 3 to 6 methylol groups and excluding the methylol group A combination of a polyhydric alcohol having 1 to 8 carbon atoms, a dihydric alcohol having the above branched structure, and a monohydric alcohol having the above branched structure is preferable.

  The blending ratio of the hydrocarbon-based alcohol and the carbonate compound is not particularly limited, but preferably (1: 1) to (1: 2) is preferable in terms of molar ratio (alcohol: carbonate compound), and (1: 1) to (1: 3). In the transesterification reaction, when the alcohol is distilled out of the system, it is preferable to charge the alcohol in excess.

  The number average molecular weight of the carbonate compound (C) is not particularly limited, but is preferably 100 to 10,000, more preferably 500 to 5,000, and still more preferably 1,000 to 2,000. . When the number average molecular weight is within the above range, the obtained polyurethane resin can be a polyurethane resin having low hardness and excellent durability.

The viscosity of the carbonate compound (C) at 25 ° C. is not particularly limited, but can be 5000 mPa · s or less, preferably 1500 mPa · s or less, particularly 1000 mPa · s or less, and more preferably 500 mPa · s or less ( Usually, 10 mPa · s or more). When this viscosity is in the above range, the obtained polyurethane resin can be made into a low-hardness polyurethane resin, and it is preferable because it is easy to handle in the production of polyurethane resins.
The viscosity of the carbonate compound can be measured by, for example, a B-type viscometer.

Preferred embodiments (combinations) of the hydrocarbon alcohol and hydrocarbon carboxylic acid for forming the carbonate compound (C) are as follows.
(1) a dihydric alcohol having a molecular weight of 300 to 900 (more preferably 300 to 800), a molecular weight of 100 to 400 (more preferably 120 to 350), a monohydric alcohol having a branched structure, and a molecular weight of 300 or less (further (Preferably 200 or less) carbonate compound.
(2) a dihydric alcohol having a molecular weight of 300 or less (further 200 or less, particularly 100 or less), and a monohydric alcohol having a molecular weight of 100 to 400 (more preferably 120 to 350) and having a branched structure; Carbonate compounds having a molecular weight of 100 or less (more preferably 50 or less).

  About the aspect of said (1), specifically, hydrogenated dimer diol obtained by complete hydrogenation of dimer acid, 1,12 hydroxystearyl alcohol, and castor oil fatty acid were reduced as hydrocarbon type dihydric alcohol. Castor alcohol and the like. Examples of the monohydric alcohol having a branched structure include isotridecanol, isodecanol, and isooctanol. Examples of the carbonate compound include diethyl carbonate, dimethyl carbonate, diphenyl carbonate, and the like.

  In the embodiment (2), specifically, as the dihydric alcohol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexane Diol, 1,6 hexanediol, 1,4 butanediol and the like can be mentioned. Examples of the monohydric alcohol having a branched structure include isohexadecanol, isooctyldodecanol, and decyltetradecanol. Examples of the carbonate compound include diethyl carbonate, dimethyl carbonate, diphenyl carbonate, and the like.

The manufacturing method of carbonate type compound (C) is not specifically limited, It can obtain by making the raw material mixture containing hydrocarbon type alcohol and a carbonate compound react. That is, it can be produced by a transesterification reaction between a hydrocarbon alcohol and a carbonate compound. The reaction conditions and the like are not particularly limited, but can be as follows, for example.
The preferable mass ratio of the hydrocarbon-based alcohol and the preferable mass ratio of the hydrocarbon-based alcohol and the hydrocarbon-based carbonate compound in the production of the carbonate-based compound (C) are as described above.

  When reacting the alcohol and the carbonate compound, it is preferable to use a catalyst used in the transesterification reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony and cerium. An alkoxide, a salt, an oxide, etc. are mentioned. In the present invention, carbonates, carboxylates, borates, silicates, oxides, organometallic compounds, etc. of metal elements such as alkali metals, alkaline earth metals, zinc, titanium and lead are used as catalysts. Of these, organic titanium compounds are particularly preferable.

Although the usage-amount of a transesterification catalyst is not specifically limited, In order to accelerate | stimulate a transesterification reaction and to raise the yield of a carbonate type compound, 5-2000 ppm in mass ratio with respect to the sum total of alcohol and a carbonate compound, In particular, it is preferably 10 to 800 ppm, more preferably 20 to 600 ppm. If the amount of the transesterification catalyst used is less than 5 ppm, the rate of the transesterification reaction becomes too low, so that a long time is required for the reaction, and the yield of the carbonate compound is also lowered. On the other hand, if it exceeds 2000 ppm, the carbonate-based compound may be colored, and the durability of the polyurethane resin produced using this compound tends to be lowered.
The transesterification catalyst remaining in the carbonate compound is preferably deactivated. The transesterification catalyst remaining in the carbonate-based compound is blended with water and a phosphorus compound in the same molar amount as this transesterification catalyst, and heated at 80 to 120 ° C., particularly 90 to 110 ° C. for 1 to 5 hours. Can be deactivated.

  The reaction conditions for the transesterification reaction are not particularly limited. For example, the temperature of the reactor charged with the raw material mixture is changed from room temperature (for example, 20-30 ° C.) to 100-280 ° C., particularly 140-260 ° C., more preferably 160-240 under normal pressure (for example, 0.098 MPa). The temperature is raised to a predetermined temperature of 8 ° C. for 8 to 24 hours, particularly 12 to 20 hours, and then the reaction is performed while maintaining the predetermined temperature in the reactor of 1 to 100 kPa, particularly 1 to 50 kPa, The pressure can be gradually reduced to 10 kPa over 2 to 8 hours, particularly 4 to 6 hours, and further reacted for 1 to 8 hours, particularly 2 to 6 hours.

  In addition, the temperature of the reactor into which the raw material mixture has been charged is reacted under a normal pressure (for example, 0.098 MPa) at a low temperature of 110 to 180 ° C., particularly 130 to 160 ° C. for 1 to 4 hours, particularly 1 to 3 hours. Thereafter, the reaction is carried out at a predetermined temperature in a high temperature range of 150 to 280 ° C., particularly 180 to 240 ° C. for 1 to 4 hours, particularly 1 to 3 hours. The pressure can be gradually reduced to 10 kPa, particularly 1 to 3 kPa over 2 to 8 hours, particularly 4 to 6 hours, and further reacted for 1 to 8 hours, particularly 2 to 6 hours.

  Furthermore, this carbonate compound has the desired structure and physical properties by adjusting the mass ratio of alcohols and carbonate compound, the type and amount of transesterification catalyst, and the reaction conditions for the transesterification reaction. The carbonate compound prepared in advance is reacted with a polyhydric alcohol, a monohydric alcohol and, if necessary, a dihydric alcohol, and at least one other polycarbonate polyol, and reacted. A carbonate compound having the structure and physical properties of the period can also be used.

The transesterification reaction is an equilibrium reaction, and it is necessary to distill off the by-produced alcohol continuously and efficiently. Therefore, it is preferable to distill off the alcohol by-produced at a predetermined temperature and the azeotrope of the alcohol and the carbonate compound in the previous reaction under normal pressure. Further, in the reaction under reduced pressure in the latter stage, the inside of the reactor is reduced from normal pressure to the above pressure at a predetermined temperature, thereby facilitating the distillation of the by-produced alcohol and the azeotrope of the alcohol and the carbonate compound. You can also Thus, in order to distill off the by-produced alcohol and azeotrope, the reactor is preferably provided with a distillation column or the like.
In any of the above reaction conditions, it is preferable to circulate an inert gas such as nitrogen gas and argon in the reactor to promote the distillation of alcohol and azeotrope by-produced.

(4) Polyol composition The polyol composition of the present invention contains the vinyl polymer (A) and at least one selected from the ester compound (B) and the carbonate compound (C).
Further, the blending mass ratio of the vinyl polymer (A) and the ester compound (B) and / or the carbonate compound (C) [vinyl polymer (A): ester compound (B) and / or Or, the carbonate compound (C)] is not particularly limited, but (5:95) to (55:45) is preferable, and (10:90) to (40:60) is more preferable. When the blending ratio is within the above range, a polyurethane resin having extremely low hardness, excellent durability, and excellent heat resistance and hydrolysis resistance can be obtained.
Further, the content of these compounds is not particularly limited, but when the total amount of the polyol composition is 100% by mass, the content of the vinyl polymer (A) is preferably 1 to 50% by mass. Yes, more preferably 5 to 45% by mass, still more preferably 10 to 40% by mass. The total content of the ester compound (B) and the carbonate compound (C) is preferably 50 to 99% by mass, more preferably 55 to 95% by mass, and still more preferably 60 to 90% by mass. %.

  The hydroxyl value of the polyol composition of the present invention is not particularly limited, but is preferably 4 to 40 mgKOH / g, more preferably 10 to 45 mgKOH / g, and particularly preferably 20 to 40 mgKOH / g. When this hydroxyl value is in the above range, the polyol composition has a viscosity that is easy to handle, has extremely low hardness, excellent durability, and can be a polyurethane resin excellent in heat resistance and hydrolysis resistance.

Furthermore, the viscosity at 25 ° C. of this polyol composition is not particularly limited, but can be 10000 mPa · s or less, preferably 5000 mPa · s or less, and particularly preferably 2000 mPa · s or less (usually 10 mPa · s or more). . If this viscosity is 10,000 mPa · s or less, it is preferable because it is easy to handle, for example, in the production of polyurethane resins.
The viscosity of this polycarbonate polyol composition can be measured by, for example, a B-type viscometer.

  The polyol composition of the present invention may further contain other polyols and other additives. Other polyols include polyether polyols, polyester polyols, polytetramethylene ether glycol, tetrahydrofuran-alkylene oxide copolymer polyols, epoxy-modified polyols, hydrocarbon polyols, partially saponified products of ethylene-vinyl acetate copolymers, difficult General purpose or special polyols such as fuel polyols, xylene skeleton polyols, vegetable oil modified polyols such as castor oil-based polyols, silicon-containing polyols fluorine-containing polyols and nitrogen-containing polyols. Although the combined proportion of these other polyols is not particularly limited, it is preferably within a range where the functions and effects of the present invention are not significantly impaired. The mass ratio of the other polyol is, for example, 30% by mass or less, particularly 20% by mass or less, more preferably 10% by mass or less, when the total amount of the polyol composition is 100% by mass, and 5% by mass or less It is more preferable that Thus, it is preferable that other polyols are as little as possible. If the content of other polyols is excessive, the heat resistance, hydrolysis resistance and the like tend to decrease. These other polyols may be used alone or in combination of two or more.

  Examples of the other additives include talc, clay, mica, kaolin, bentonite, calcium carbonate, silica, alumina, titania, aluminum hydroxide, carbon black, graphite, glass fiber, carbon fiber and other inorganic fillers or pigments, dioctyl Examples thereof include phthalate ester plasticizers such as phthalate, adipic acid plasticizers such as dioctyl adipate, and plasticizers such as phosphate ester plasticizers and polyester plasticizers.

  In addition, oils and fats such as hemp seed oil, linseed oil, poppy oil, tung oil, rapeseed oil and tall oil, flame retardants such as phosphorus compounds, halogen compounds and antimony oxide, diluents such as methylacetylated ricinoleate and trimethyl phosphate, Organic solvents, ultraviolet absorbers, antioxidants, anti-aging agents, coupling agents, surfactants, antifoaming agents, mold release agents, resins such as xylene resins, rosins, rosin esters, terpene resins and petroleum resins, perfumes And antifungal agents. Only 1 type may be used for these additives etc., and 2 or more types may be used for them.

  The method for producing the polyol composition of the present invention is not particularly limited. The vinyl polymer (A), the ester compound (B), and / or the carbonate compound (C) may be mixed and manufactured by a mixing method using a normal mixing device. can do. As the mixing device, various mixers, screw extruders, and the like can be used.

[2] Polyurethane resin The polyurethane resin of the present invention is obtained by reacting a polyol component containing a polyol composition with a polyisocyanate component. As the polyol composition contained in the polyol component, the polyol composition of the present invention can be used, and the above description can be applied as it is to this polyol composition.

  The polyisocyanate is not particularly limited, and various compounds such as polyisocyanate can be used. Examples of the polyisocyanate compound include 2,4- or 2,6-tolylene diisocyanate, 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 2, 2,4- or 2,4,4-trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 1,3-or 1,4-xylylene diisocyanate, 1,3- or 1,4-tetramethylxylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, norbornene diisocyanate, trans-1,4-cyclohexyl diisocyanate, lysine dii Cyanate, lysine triisocyanate, methylcyclohexane-2,4- or 2,6-diisocyanate, 1,3- or 1,4- (diisocyanatemethyl) cyclohexane, dianisidine diisocyanate, dimer acid diisocyanate, isopropylidenebis (4-cyclohexyl) Isocyanate), triphenylmethane diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris (isocyanatephenyl) -thiophosphoric acid, and other monomeric or polymeric materials can be used.

  Further, urethane-modified products, allophanate-modified products, biuret-modified products, carbodiimide-modified products, uretonimine-modified products, uretdione-modified products (dimers), isocyanurate-modified products, urea-modified products, acylated urea-modified products, and Blocked products (phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite, boric acid, etc.) as well as normal A prepolymer or the like can also be used. For example, carbodiimide-modified diphenylmethane diisocyanate, polymerized diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like can be used. Only one type of polyisocyanate may be used, or two or more types may be used.

  The prepolymer may be an NCO-terminated prepolymer or an OH-terminated prepolymer. Thus, the polycarbonate polyol composition of the present invention can be used as a prepolymer for producing a polyurethane resin. Further, the NCO-terminated prepolymer can be blocked with the above-mentioned blocking agent, and this blocked NCO-terminated prepolymer can be used for producing a polyurethane resin.

  The polyol component may further contain other polyols. About this other polyol, the description of the other polyol in the said polyol composition is applicable as it is.

  A catalyst, a crosslinking agent, a chain extender, etc. can be mix | blended with a polyol component and the said polyisocyanate component. Moreover, when a polyurethane resin is a foam, a foaming agent, a foam stabilizer, etc. can also be mix | blended. A catalyst, a crosslinking agent, a chain extender, a foaming agent, a foam stabilizer and the like may be blended in the polyol component or in the polyisocyanate component. Furthermore, you may mix | blend with both a polyol component and a polyisocyanate component. Usually, the catalyst, the cross-linking agent, the chain extender and the foaming agent are often blended with the polyol component, and the foam stabilizer is often blended with the polyisocyanate component.

As the catalyst, at least one of a metal catalyst and an amine catalyst can be used. In the mold forming in which it is preferable to use a raw material having a relatively slow reaction, a metal catalyst is usually used. On the other hand, in field construction or the like, an amine catalyst having a relatively fast reaction is often used, and an amine catalyst and a metal catalyst can be used in combination.
Examples of the metal catalyst include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, and lead octenoate. The compounding amount of the metal catalyst can be 0.005 to 2 parts by mass, particularly 0.01 to 0.5 parts by mass, when the total amount of polyol is 100 parts by mass. Only one metal catalyst may be used, or two or more metal catalysts may be used.

  Examples of amine catalysts include triethylamine, N, N-dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylpropane-1,3-diamine, tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, tetramethylguanidine, N -Methylmorpholine, dimethylmethylenediamine, dimethylaminoethanol and the like. The compounding amount of the amine catalyst can be 1 to 3 parts by mass, particularly 0.5 to 2.5 parts by mass, when the total amount of polyol is 100 parts by mass. Only one type of amine catalyst may be used, or two or more types may be used.

  As the crosslinking agent or chain extender, diol, triol, tetraol, diamine, amino alcohol and the like can be used. Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and 1,4-butanediol. Examples of the triol include glycerin and trimethylolpropane. Examples of tetraol include bentaerythritol. Furthermore, examples of the diamine include hexamethylene diamine. Examples of the amino alcohol include diethanolamine. The amount of the crosslinking agent or chain extender may be 1 to 10 parts by mass when the total amount of polyol is 100 parts by mass. Only one type of crosslinking agent or chain extender may be used, or two or more types may be used.

  As the foaming agent, water, a low boiling point compound or the like is usually used. Moreover, water and carbon dioxide are usually used in combination, particularly in spraying construction in field construction. The blending amount of this foaming agent may be appropriately set according to the predetermined foaming ratio of the foam, etc. For example, water is 0.2 to 8 parts by mass, especially when the polyol is 100 parts by mass, It can be 1-5 mass parts. Further, as the foam stabilizer, a linear or branched polyether-siloxane copolymer or the like can be used. The blending amount of the foam stabilizer can be 0.5 to 2 parts by mass when the polyol is 100 parts by mass. Only one type of foam stabilizer may be used, or two or more types may be used.

  A flame retardant can be mix | blended with a polyol component to a polycarbonate polyol composition as mentioned above. Moreover, this flame retardant can also be mix | blended when mixing polyols, such as a polycarbonate polyol composition, a catalyst, a crosslinking agent, etc. Further, the flame retardant can be contained in the polyisocyanate component. In particular, when used for a heat insulating wall of a building, it is preferable to add a flame retardant.

  Examples of the flame retardant include phosphorus compounds, halogen compounds, and antimony oxide as described above. Examples of the phosphorus compound include phosphate ester compounds, ammonium polyphosphate, and phosphine. Examples of the halogen compound include tris (2,3-dichloropropyl) phosphonate, neopentyl brominated polyether, dibromopropanol, and dibromoneopentyl glycol. As the flame retardant, aluminum hydroxide, magnesium hydroxide, metal / amine complex, or the like can be used. As the flame retardant, a phosphate ester flame retardant having no halogen is more preferable.

  The blending ratio of the polyol and the polyisocyanate, that is, the isocyanate index (NCO / OH equivalent ratio) is not particularly limited, but is 0.7 to 1.6, particularly 0.8 to 1.4, more preferably 0.9 to 1. .2 is preferable. When the isocyanate index is less than 0.7 or exceeds 1.6, the heat resistance, water resistance, flexibility and the like of the resulting polyurethane resin tend to decrease.

The C hardness of the polyurethane resin measured at 23 ° C. (hardness measured using a type C durometer) is not particularly limited, but is preferably 0C to 10C, particularly 0C to 5C, and more preferably 0C to 3C. Thus, if it is a polyurethane resin having extremely low hardness, excellent durability, heat resistance, hydrolysis resistance, etc., sealing materials and coating materials, casting materials, sealing materials for protecting electronic parts, etc. It is particularly useful in various applications such as vibration damping materials and pressure-sensitive adhesives.
The hardness of this polyurethane resin can be measured according to JIS K 7312. Specifically, it can be measured by using a type C durometer, pressing a test piece perpendicularly to a needle at 23 ° C. with a pressing force of 1 N, and immediately reading the hardness value.

  The polyurethane resin may contain various additives. These various additives may be added to the polycarbonate polyol composition as described above, or various additives may be added to at least one of the polyol component and the polyisocyanate component. Moreover, you may mix | blend with the manufactured polyurethane resin.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the synthesis examples, examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified. In addition, the number average molecular weight (hereinafter also referred to as “Mn”) in Synthesis Examples, Examples, and Comparative Examples was measured by GPC under the following measurement conditions.
(1) Apparatus; “Shodex GPC-104” (manufactured by Showa Denko KK)
(1) Column: “Shodex KF-602” (manufactured by Showa Denko KK)
(2) Column temperature; 40 ° C
(3) Eluent: THF
(4) Detector: Differential refractive index detector (5) Detector temperature: 40 ° C
(6) Standard material: Polystyrene

In addition, the calculated number of hydroxyl groups (average number of hydroxyl groups), which is the number of hydroxyl groups (the number of theoretical hydroxyl groups) of the vinyl polymer, ester compound, and carbonate compound product obtained by the synthesis example, is calculated by the following formula. And the number of hydroxyl groups calculated in the same manner as in the above formulas (1) to (3) (calculated hydroxyl number).
Calculated number of hydroxyl groups (theoretical number of hydroxyl groups) = number average molecular weight of the product / mixture (mole) ratio of raw materials forming the product and molecular weight per hydroxyl group calculated from the molecular weight

[1] Synthesis of vinyl polymer A Synthesis of vinyl polymer A1 A reactor equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser was charged with 500 g of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate. 29 g, 170 g of isopropyl alcohol, and 1.0 g of 2,2′-azobisisobutyronitrile were charged and heated with stirring at normal pressure (0.098 MPa) under a nitrogen stream. Spontaneous heat generation occurred from around 70 ° C., and the reaction was performed for 6 hours while refluxing isopropyl alcohol. Thereafter, the reflux condenser was removed and isopropyl alcohol was recovered. Thus, the hydroxyl number of the vinyl polymer calculated from the hydroxyl value of 30 mgKOH / g, the viscosity of 140,000 mPa · s / 25 ° C., the number average molecular weight of 6600 by GPC measurement, and the blending ratio and number average molecular weight of the raw materials used was ( Hereinafter, it is referred to as “calculated number of hydroxyl groups”.) 3 vinyl polymer A1 was obtained. Table 1 shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained vinyl polymer A1.

Synthesis of vinyl polymer A2 A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was added to 500 g of 2-ethylhexyl acrylate, 56 g of 2-hydroxyethyl acrylate, 170 g of isopropyl alcohol, and 2,2. '-Azobisisobutyronitrile (1.0 g) was charged and heated with stirring at normal pressure (0.098 MPa) under a nitrogen stream. Spontaneous heat generation occurred from around 70 ° C., and the reaction was performed for 6 hours while refluxing isopropyl alcohol. Thereafter, the reflux condenser was removed and isopropyl alcohol was recovered. As a result, a vinyl polymer A2 having a hydroxyl value of 50 mgKOH / g, a viscosity of 240,000 mPa · s / 25 ° C., a number average molecular weight of 6800 by GPC measurement, and a calculated hydroxyl number of 6 was obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained vinyl polymer A2.

Synthesis of vinyl polymer A3 A reactor equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser was added to 500 g of 2-ethylhexyl acrylate, 20 g of 2-hydroxyethyl acrylate, 170 g of isopropyl alcohol, and 2,2. '-Azobisisobutyronitrile (1.0 g) was charged and heated with stirring at normal pressure (0.098 MPa) under a nitrogen stream. Spontaneous heat generation occurred from around 70 ° C., and the reaction was performed for 6 hours while refluxing isopropyl alcohol. Thereafter, the reflux condenser was removed and isopropyl alcohol was recovered. As a result, a vinyl polymer A2 having a hydroxyl value of 19 mgKOH / g, a viscosity of 10,000 mPa · s / 25 ° C., a number average molecular weight of 6300 by GPC measurement, and a calculated hydroxyl number of 2 was obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained vinyl polymer A3.

[2] Synthesis of ester compound B Preparation of ester compound B1 In a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser with a sample tube, 560 g of hydrogenated dimer diol (m1), 490 g of isostearic acid, and As a catalyst, 0.2 g of p-toluenesulfonic acid was charged and allowed to react for 10 hours at 180 to 200 ° C. under normal pressure (0.098 MPa) under a nitrogen stream. During this time, water produced by the condensation reaction was distilled out of the system. Thus, an ester compound comprising a liquid composition having an acid value of 0.2 mg KOH / g, a hydroxyl value of 15 mg KOH / g, a viscosity of 340 mPa · s / 25 ° C., a GPC measurement number average molecular weight of 1500, and a calculated hydroxyl number of 0.4. B1 was obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained ester compound B1.
The hydrogenated dimer diol (m1) is PRIPOL 2033 manufactured by Croda Japan.

Synthesis of ester compound B2 To a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser with a sample tube, 701 g of castor oil fatty acid, 582 g of isostearic acid, 200 g of 2,4-diethyl-1,5-pentanediol, In addition, 0.3 g of p-toluenesulfonic acid was charged as a catalyst, and reacted at 180 to 200 ° C. under normal pressure (0.098 MPa) under a nitrogen stream. During this time, water produced by the condensation reaction was distilled out of the system. Thus, an ester compound B2 comprising a liquid composition having an acid value of 0.6 mgKOH / g, a hydroxyl value of 17 mgKOH / g, a viscosity of 260 mPa · s / 25 ° C., a number average molecular weight of 1200 by GPC measurement, and a calculated hydroxyl number of 0.4 is obtained. Obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained ester compound B2.

Synthesis of ester compound B3 A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser with a water sampling tube, 701 g of castor oil fatty acid, 582 g of isostearic acid, 130 g of trimethylolpropane, and p-toluenesulfonic acid 0 as a catalyst .3 g was charged and allowed to react at normal pressure (0.098 MPa) at 180 to 200 ° C. for 10 hours under a nitrogen stream. During this time, water produced by the condensation reaction was distilled out of the system. Thus, an ester compound B3 composed of a liquid composition having an acid value of 1.8 mgKOH / g, a hydroxyl value of 26 mgKOH / g, a viscosity of 460 mPa · s / 25 ° C., a number average molecular weight of 1300 by GPC measurement, and a calculated hydroxyl number of 0.7 is obtained. Obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained ester compound B3.

Synthesis of ester compound B4 A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser with a test tube, 701 g of castor oil fatty acid, 494 g of isostearic acid, 303 g of trimethylolpropane, and p-toluenesulfonic acid 0 as a catalyst .3 g was charged and allowed to react at normal pressure (0.098 MPa) at 180 to 200 ° C. for 10 hours under a nitrogen stream. During this time, water produced by the condensation reaction was distilled out of the system. As a result, an ester compound B4 composed of a liquid composition having an acid value of 1.1 mgKOH / g, a hydroxyl value of 89 mgKOH / g, a viscosity of 620 mPa · s / 25 ° C., a number average molecular weight of 700 by GPC measurement, and a calculated hydroxyl number of 2 is obtained. It was. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained ester compound B4.

[3] Synthesis of carbonate-based compound C Synthesis of carbonate-based compound C1 In a reactor equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser with a sample tube, 580 g of hydrogenated dimer diol (m2), 300 g of isotridecanol In addition, 360 g of diethyl carbonate and 0.3 g of tetraisopropyl titanate as a catalyst were charged, heated at normal pressure (0.098 MPa) under a nitrogen stream, and the temperature was raised from room temperature (23 ° C.) to 200 ° C. over 10 hours. I let you. During this time, ethanol produced by the condensation reaction was distilled out of the system. Thereafter, the pressure in the reactor was gradually reduced, and the pressure was reduced to 30 kPa in 5 hours, and the reaction was continued for further 4 hours. As a result, a carbonate compound C1 comprising a liquid composition having an acid value of 0.2 mg KOH / g, a hydroxyl value of 29 mg KOH / g, a viscosity of 500 mPa · s / 25 ° C., a number average molecular weight of 1000 by GPC measurement, and a calculated hydroxyl number of 0.5 is obtained. Obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the ester compound C1 obtained.
The hydrogenated dimer diol (m2) is PRIPOL 2033 manufactured by Croda Japan.

Synthesis of carbonate-based compound C2 A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser with a test tube was added to 160 g of 2,4-diethyl-1,5-pentanediol, 370 g of isohexadecanol and 360 g of diethyl carbonate. Then, 0.3 g of tetraisopropyl titanate was charged as a catalyst, heated at normal pressure (0.098 MPa) under a nitrogen stream, and allowed to react from room temperature (23 ° C.) to 200 ° C. over 10 hours. During this time, ethanol produced by the condensation reaction was distilled out of the system. Thereafter, the pressure in the reactor was gradually reduced, and the pressure was reduced to 30 kPa in 5 hours, and the reaction was continued for further 4 hours. Thus, a carbonate compound C2 comprising a liquid composition having an acid value of 0.2 mg KOH / g, a hydroxyl value of 32 mg KOH / g, a viscosity of 200 mPa · s / 25 ° C., a number average molecular weight of 700 by GPC measurement, and a calculated hydroxyl number of 0.4. Obtained. Table 1 also shows the hydroxyl value, viscosity, number average molecular weight, and calculated hydroxyl number of the obtained ester compound C2.

[4] Production of Polyol Composition and Polyurethane Resin The polyol compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared according to the types and compounding amounts of the compounds shown in Table 2 below. The hydroxyl values of the polyol compositions of Examples 1 to 7 and Comparative Examples 1 to 4 are also shown in Table 2.
Then, 100 parts by mass of each polyol composition of Examples 1 to 7 and Comparative Examples 1 to 4, and liquid diphenylmethane diisocyanate (liquid MDI, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Millionate MTL”), NCO / OH equivalent The ratio is set to 1, and 0.3 parts by mass of hindered phenol (manufactured by Ciba Japan Co., Ltd., trade name “IRUGASTAB PUR68”) as an antioxidant is mixed and stirred to obtain a resin raw material. Prepared. Then, this resin raw material was cast and heated at 85 ° C. for 16 hours to be cured. In this way, a disk-shaped test piece having a diameter of 50 mm and a thickness of 10 mm was produced. In Table 2, the ester compound “DOP” used in Comparative Example 1 is dioctyl phthalate.

[5] Physical property evaluation (a) Urethane appearance evaluation: The appearance of the test piece was visually observed, and the appearance of the obtained polyurethane resin was evaluated according to the following criteria.
When the shape was maintained in a uniform state, it was considered good.
A case where a non-uniform state or shape such as a bleed was not maintained was regarded as defective.
The evaluation results are also shown in Table 2.
(B) Hardness: According to JIS K 7312, using a type C durometer, the test piece was pressed perpendicularly to the needle with a pressing force of 1 N at 23 ° C., and the hardness value was read immediately. The results are also shown in Table 2.
(C) Heat resistance (change in hardness): The test piece was left in a heating furnace adjusted to 130 ° C. for 500 hours, then taken out of the heating furnace and allowed to cool, and the same as (a) above at 23 ° C. The hardness was measured. In Table 2 below, the left side of → is the hardness before processing (130 ° C., 500 hours), and the right side is the hardness after processing. The results are also shown in Table 2. In addition, in the heat resistance test, the test piece whose shape did not retain its shape was incapable of measuring the hardness.
(D) Heat resistance (weight change rate): The test piece was left in a heating furnace adjusted to 130 ° C. for 500 hours, and then taken out of the heating furnace and allowed to cool. The weight of the test piece before treatment and the weight of the test piece after treatment were measured, and the weight change rate was calculated by the following formula for calculating the weight change rate. The results are also shown in Table 2.
Weight change rate (%) = [(weight after treatment−weight before treatment) / weight before treatment] × 100
(E) Hydrolysis resistance (change in hardness): The test piece was allowed to stand in a room at 121 ° C., an atmospheric pressure of 0.2 MPa, and a humidity of 100% to maintain the shape. The results are also shown in Table 2.
Further, “> 280” in Table 2 means that the shape is retained for more than 280 hours.

According to the results in Table 2, none of the polyurethane resins of Examples 1 to 7 produced bleed, and the polyurethane resin obtained by using the polyol composition of the present invention reliably produced bleed. It turns out that it is suppressed.
Further, in terms of hardness, all of the polyurethane resins of Examples 1 to 7 have a C hardness value of 0, and the polyurethane resin obtained by using the polyol composition of the present invention is an extremely low hardness polyurethane resin. I understand that there is.
In addition, in the heat resistance, none of the polyurethane resins of Examples 1 to 7 showed a change in hardness, and the weight change rate also showed a low value of −1.4 (Example 4) or less. This shows that the polyurethane resin obtained by using the polyol composition of the present invention is a polyurethane resin excellent in heat resistance.
Furthermore, in the hydrolysis resistance, the polyurethane resins of Examples 1 to 7 retain the shape for a relatively long time even under high temperature, high pressure and high humidity. This shows that the polyurethane resin obtained by using the polyol composition of the present invention is a polyurethane resin excellent in hydrolysis resistance.

On the other hand, in Comparative Example 1, bleeding occurred in the appearance of the obtained polyurethane resin. Further, the hardness value was 20, which was a considerably hard polyurethane resin as compared with the examples. Furthermore, it turns out that it is inferior also in heat resistance and hydrolysis resistance.
In Comparative Example 2, the polyurethane resin of the test piece was in a poorly cured state, and it was confirmed that the hydroxyl group-containing vinyl polymer was necessary for maintaining the shape of the polyurethane resin.
Moreover, in the comparative example 3, it turns out that the polyurethane resin of a test piece is inferior in heat resistance and hydrolysis resistance.
Moreover, in the comparative example 4, the polyurethane resin of the test piece was a considerably hard polyurethane resin compared with the polyurethane resin of Examples 1-7.

Claims (9)

A polyol composition containing a vinyl polymer (A) having a hydroxyl group, an ester compound (B) and / or a carbonate compound (C),
The vinyl polymer (A) has a hydroxyl value of 20 to 100 mgKOH / g,
The ester compound (B) is obtained by reacting a hydrocarbon alcohol and a hydrocarbon carboxylic acid, and has a hydroxyl value larger than 0 mgKOH / g and 60 mgKOH / g or less,
The above-mentioned carbonate compound (C) is obtained by reacting a hydrocarbon alcohol and a carbonate compound, and has a hydroxyl value of more than 0 mgKOH / g and 60 mgKOH / g or less.   The polyol composition according to claim 1, wherein the vinyl polymer (A) has 3 or more hydroxyl groups.   The polyol composition according to claim 1 or 2, wherein the number average molecular weight of the ester compound (B) and the carbonate compound (C) is 600 or more.   The polyol composition according to any one of claims 1 to 3, wherein the hydrocarbon alcohol and the hydrocarbon carboxylic acid have a molecular weight of 100 or more.   The polyol composition according to any one of claims 1 to 4, wherein at least one of the hydrocarbon alcohol and the hydrocarbon carboxylic acid has a branched structure.   The polyol composition according to any one of claims 1 to 5, wherein the polyol composition has a hydroxyl value of 4 to 40 mgKOH / g.   The polyol according to any one of claims 1 to 6, wherein the vinyl polymer (A) contains a structural unit derived from a (meth) acrylic acid hydroxyalkyl ester and a structural unit derived from a (meth) acrylic acid alkyl ester. Composition.   The polyol composition according to any one of claims 1 to 7, wherein the content of the vinyl polymer (A) is 1 to 50% by mass when the total amount of the polyol composition is 100% by mass.   A polyurethane resin obtained by using a raw material component comprising a polyol component containing the polyol composition according to any one of claims 1 to 8 and a polyisocyanate component.