WO2019008800A1

WO2019008800A1 - Polyol composition and coating composition

Info

Publication number: WO2019008800A1
Application number: PCT/JP2018/000516
Authority: WO
Inventors: 謙太川岸; 雅実飯場; 豪藤澤; 富夫凪
Original assignee: 伊藤製油株式会社; サンユレック株式会社
Priority date: 2017-07-05
Filing date: 2018-01-11
Publication date: 2019-01-10
Also published as: JP2019014803A; JP6537078B2

Abstract

This polyol composition is characterized by the inclusion of: (A) a polyol comprising a compound whereof the molecular weight is less than 500, having an ester bond and two or more hydroxy groups, the average number of hydroxy groups per molecule being 2.2 or more, and (B) a polyol comprising a compound whereof the molecular weight is less than 450, having no ester bond but having an aromatic hydrocarbon group or an alicyclic hydrocarbon group and two or more hydroxy groups. This coating composition is characterized by the inclusion of the aforementioned polyol composition and a polyisocyanate, where the ratio of the total amount in moles of isocyanate groups derived from the polyisocyanate with respect to the total amount in moles of hydroxy groups derived from the polyol composition is 0.8 to 1.1.

Description

Polyol composition and paint composition

The present invention relates to a coating composition having a self-repairing function and providing a dry film having a durometer hardness of 60 or more (hereinafter simply referred to as "coating") and a polyol composition used for the preparation thereof. The "self-healing function" refers to an action of scratching or denting caused by pressure or the like temporarily exists as a scratch as compared with other flat portions, but the wound is repaired by the nature of the film.

For example, a coating (hard coating treatment or the like) may be applied to the surface of a resin material or an inorganic material which has low hardness and is easily scratched to form a film having excellent scratch resistance. However, once a small scratch is attached to the surface, it is often impossible to replace the scratch itself.
In recent years, a technique for imparting a self-repairing function to a film to enhance scratch resistance is required, for example, Patent Document 1 discloses allophanate having a weight average molecular weight of 1000 to 3000 and an isocyanate group content of 10 to 25% by mass. A composition comprising a reaction product of a group-containing polyisocyanate (A) and an alcohol compound (B) having a weight average molecular weight of 100 to 5,000, a hydroxyl value of 20 to 600 mg KOH / g and a hydroxyl number of 1 to 5. There is disclosed an additive composition for a paint which improves the transparency of the film and improves the self-repairing function of the film, and a paint composition containing the same.

JP, 2016-27113, A

When the surface of a film obtained using the coating composition described in Patent Document 1 is scratched, it has been necessary to heat the film to 50 ° C. or higher in order to exhibit a self-repairing function. In addition, when the durometer hardness of this film is low, for example, if it is 55 or less, it tends to bring tack to the surface, and if an abrasion occurs, the film of the scratch is destroyed and the self-repairing function It was sometimes difficult to get it back.
The present invention is a coating composition which gives a film having a durometer hardness of 60 or more, and when the surface of the film is scratched, by leaving it in an atmosphere of less than 50.degree. C., for example 20.degree. C. to 45.degree. An object of the present invention is to provide a coating composition which can provide a good self-repairing function. Another object of the present invention is to provide a polyol composition suitable for the preparation of the above-mentioned coating composition.

The present invention is as follows.
1. (A) a polyol having an ester bond and two or more hydroxy groups and having a molecular weight of less than 500, and having an average number of hydroxy groups per molecule of 2.2 or more, and (B) an ester bond A polyol composition comprising a polyol which does not have an aromatic hydrocarbon group or an alicyclic hydrocarbon group and two or more hydroxy groups and has a molecular weight of less than 450.
2. The polyol composition according to Item 1, wherein the polyol (A) is a condensate of a polyhydric alcohol and a dibasic acid.
3. The polyol (A) is an aliphatic compound comprising a condensate of a first polyhydric alcohol having two hydroxy groups, a second polyhydric alcohol having three or more hydroxy groups, and a dibasic acid. The polyol composition according to Item 2.
4. The polyol composition according to any one of Items 1 to 3, wherein the polyol (B) is a diol.
5. 5. The polyol composition according to item 4, wherein the diol is at least one selected from a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

(Wherein, R ¹ and R ² are each independently an aliphatic hydrocarbon group having 2 to 4 carbon atoms, and R ³ and R ⁴ are each independently having 1 to ⁴ carbon atoms And m1 and m2 are each independently an integer of 0 to 3, and n1, n2 and n3 are each independently 0 or 1).

(Wherein, R ⁵ , R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and p 1, p 2, p 3 and p 4 are each independently of each other) And q 1 and q 2 are each independently an integer of 0 to 6.)
6. The content ratio of the said polyol (A) and said polyol (B) is 55-93 mass% and 7-45 mass%, respectively, when the sum total of both is 100 mass%. Polyol composition according to any one of the preceding claims.
7. 7. The polyol composition according to any one of the above items 1 to 6, wherein the average number of hydroxy groups in the polyol composition is 2.2 to 3.5, and the average hydroxyl value is 350 to 600 mg KOH / g.
8. The polyol composition according to any one of the above items 1 to 7, and a polyisocyanate.
A coating composition characterized in that a ratio of a total molar amount of isocyanate groups derived from the polyisocyanate to a total molar amount of hydroxy groups derived from the polyol composition is 0.8 to 1.1.
9. 9. The coating composition according to item 8, wherein the average number of isocyanate groups per molecule of the polyisocyanate is 3.0 to 4.0.
10. 10. The paint composition according to item 8 or 9, wherein the polyisocyanate has an allophanate bond.
11. 11. The coating composition according to any one of the above items 8 to 10, wherein the resulting film has a self-repairing function.

According to the coating composition of the present invention, a coating having a durometer hardness of 60 or more can be easily obtained. When the surface of the film is scratched, a good self-healing function can be obtained by leaving it in an atmosphere of less than 50 ° C., for example, 20 ° C. to 45 ° C.
The polyol composition of the present invention is a raw material component of a coating composition which has a self-repairing function and provides a film having a durometer hardness of 60 or more by combining it with a polyisocyanate and forming an isocyanate index within a specific range. Is preferred.

The polyol composition of the present invention comprises a compound having a (A) ester bond and two or more hydroxy groups and having a molecular weight of less than 500, and having an average number of hydroxy groups per molecule of 2.2 or more, And (B) containing a polyol comprising a compound having no ester bond, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and two or more hydroxy groups and having a molecular weight of less than 450. It is characterized by The polyol composition of the present invention can contain other polyols, monools, various additives and the like except the above-mentioned polyols (A) and (B) as long as the effect is not reduced.
Further, the polyol composition of the present invention is preferably a composition to be blended in a coating composition that forms a film having a self-repairing function.

The polyol (A) is a polyester polyol composed of a compound having an ester bond and two or more hydroxy groups and having a molecular weight of less than 500. The polyol (A) may be any of an aromatic polyester polyol, an alicyclic polyester polyol and an aliphatic polyester polyol. In addition, the polyol (A) contained in the polyol composition of the present invention may be only one type or two or more types, but the average number of hydroxy groups per molecule is 2.2 or more. is there.

The polyol (A) is preferably a condensate obtained from a polyhydric alcohol and a dibasic acid, or a condensate obtained from a polyhydric alcohol and a hydroxycarboxylic acid.
These condensates can be those obtained by conventional condensation reactions.

Among the above polyhydric alcohols, as a diol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8- Octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol , Tripropylene glycol, polyoxyp Aliphatic diols such as (poly) alkylene glycols such as pyrene glycol, ditetramethylene glycol and polytetramethylene ether glycol; cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol, cycloheptane diol, cyclooctane diol, 1,4-cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5,2,1,0 ^2,6] decane - di Methanol, bicyclo [4.3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1 , 1] Dodecane-Jie , Hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol, 2,2-bis- (4- Alicyclic diols such as hydroxycyclohexyl) propane and 1,3-adamantanediol; and alkylene oxides such as ethylene oxide and propylene oxide added to hydroquinone, resorcinol, dihydroxyphenyl, naphthalenediol, dihydroxydiphenyl ether, bisphenol A and bisphenol A Adducts (such as diethoxylated bisphenol A), p-xylylene glycol, m-xylylene glycol, o-xylylene glycol, 4,4'-bishydroxymethylbiphenyl, 4,2 ' Aromatic diols such as bishydroxymethylbiphenyl, 2,2'-bishydroxymethylbiphenyl, 4,3'-bishydroxymethylbiphenyl, 3,3'-bishydroxymethylbiphenyl, 3,2'-bishydroxymethylbiphenyl It can be mentioned.
Further, among the above polyhydric alcohols, as the polyol having three or more hydroxy groups, aliphatic triols such as glycerin, trimethylolpropane, trimethylolethane, alkanetriols such as hexanetriol, etc .; pentaerythritol, sorbitol, mannitol, sorbitan And aliphatic polyols such as alkane polyols such as diglycerin and dipentaerythritol.
Among the above compounds, the polyol (A) may be obtained using only one of polyhydric alcohols, or may be obtained using two or more in combination. .

The dibasic acid may be any of aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alicyclic dicarboxylic acids.
The above aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid And octadecanedioic acid.
As the above aromatic dicarboxylic acid, p-phenylenediacetic acid, orthophthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1,8-naphthalenedicarboxylic acid, 1,4- Naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid (diphenic acid), 3,3'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid 4,4'-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxy) Phenyl) propane, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid 3,3'-Carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'- Terephthaloyl dibenzoic acid and the like can be mentioned.
Examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,4-cyclohexanediacetic acid.

When the polyol (A) is a condensate obtained from a polyhydric alcohol and a dibasic acid, the number of polyhydric alcohol and dibasic acid used to form the condensate is only one. It may be two or more.

2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxy-2-methylpropanoic acid, and 2-hydroxybutanoic acid -2-Methylbutanoic acid, 2-hydroxy-2-ethylbutanoic acid, 2-hydroxy-2-methylpentanoic acid, 2-hydroxy-2-ethylpentanoic acid, 2-hydroxy-2-propylpentanoic acid, 2-hydroxy-2 -Butylpentanoic acid, 2-hydroxy-2-methylhexanoic acid, 2-hydroxy-2-ethylhexanoic acid, 2-hydroxy-2-propylhexanoic acid, 2-hydroxy-2-butylhexanoic acid, 2-hydroxy-2 -Pentylhexanoic acid, 2-hydroxy-2-methylheptanoic acid, 2-hydric acid Hydroxy-2-methylheptanoic acid, 2-hydroxy-2-ethyl heptanoic acid, 2-hydroxy-2-propyl heptanoic acid, 2-hydroxy-2-butyl heptanoic acid, 2-hydroxy-2-pentyl heptanoic acid, 2- Hydroxy-2-hexylheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 2-hydroxy-2-ethyloctanoic acid, 2-hydroxy-2-propyloctanoic acid, 2-hydroxy-2-butyloctanoic acid, 2- Hydroxy-2-pentyloctanoic acid, 2-hydroxy-2-hexyloctanoic acid, 2-hydroxy-2-heptyloctanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 3-hydroxypentanoic acid, 3-hydroxyhexane Acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydro Ci-3-methylbutanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-hydroxy-3-ethylpentanoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-3-ethylhexanoic acid, 3-hydroxy 3-Propylhexanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3-ethylheptanoic acid, 3-hydroxy-3-propylheptanoic acid, 3-hydroxy-3-butylheptanoic acid, 3-hydroxy -3-Methyloctanoic acid, 3-hydroxy-3-ethyloctanoic acid, 3-hydroxy-3-propyloctanoic acid, 3-hydroxy-3-butyloctanoic acid, 3-hydroxy-3-pentyloctanoic acid, 4-hydroxy Butanoic acid, 4-hydroxypentanoic acid, 4-hydroxyhexanoic acid, 4-hydroxyheptanoic acid, 4-hydroxyoctanoic acid, 4-hydroxy-4-methylpentanoic acid, 4-hydroxy-4-methylhexanoic acid, 4-hydroxy-4-ethylhexanoic acid, 4-hydroxy-4-methylheptanoic acid, 4-hydroxy- 4-ethylheptanoic acid, 4-hydroxy-4-propylheptanoic acid, 4-hydroxy-4-methyloctanoic acid, 4-hydroxy-4-ethyloctanoic acid, 4-hydroxy-4-propyloctanoic acid, 4-hydroxy- 4-Butyloctanoic acid, 5-hydroxypentanoic acid, 5-hydroxyhexanoic acid, 5-hydroxyheptanoic acid, 5-hydroxyoctanoic acid, 5-hydroxy-5-methylhexanoic acid, 5-hydroxy-5-methylheptanoic acid, 5-hydroxy-5-ethylheptanoic acid, 5-hydroxy-5-methyloctanoic acid, -Hydroxy-5-ethyloctanoic acid, 5-hydroxy-5-propyloctanoic acid, 6-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 6-hydroxyoctanoic acid, 6-hydroxy-6-methylheptanoic acid, 6-hydroxy -6-methyloctanoic acid, 6-hydroxy-6-ethyloctanoic acid, 7-hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 7-hydroxy-7-methyloctanoic acid, 8-hydroxyoctanoic acid, 8-hydroxystearic acid 9-hydroxystearic acid, 10-hydroxystearic acid, 11-hydroxystearic acid, 12-hydroxystearic acid, 8-hydroxypalmitic acid, 9-hydroxypalmitic acid, 10-hydroxypalmitic acid, 11-hydroxypalmitic acid, 12 -Hydroxypa Mytic acid, ricinoleic acid (ricinoleic acid), castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, 2-hydroxynaphthalene-3-carboxylic acid, 2-hydroxynaphthalene-6-carboxylic acid, Examples thereof include 2,2-dimethylol propionic acid, 2,2-dimethylol valeric acid, 2,2- dimethylol pentanoic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxide decanoic acid and the like.

When the polyol (A) is a condensate obtained from a polyhydric alcohol and a hydroxycarboxylic acid, the number of polyhydric alcohol and hydroxycarboxylic acid used for forming the condensate is only one. It may be two or more.

In the present invention, the polyol (A) is preferably a condensate of a polyhydric alcohol and a dibasic acid. At this time, the polyhydric alcohol is preferably a compound having 2 to 10 carbon atoms, and the dibasic acid is preferably a compound having 4 to 12 carbon atoms.
In the present invention, the polyol (A) is particularly preferably a first polyhydric alcohol having two hydroxy groups, a second polyhydric alcohol having three or more hydroxy groups, and a dibasic acid. An aliphatic compound consisting of a condensate of The first polyhydric alcohol is preferably a compound having 2 to 6 carbon atoms, and the second polyhydric alcohol is preferably a compound having 3 to 10 carbon atoms.

The polyol (A) according to the present invention has a self-repairing function and has a durometer hardness of 60 or more by the coating composition having the specific range of isocyanate index, which contains the polyol (B) and the polyisocyanate together. The polyol composition of the present invention contains a polyol (A) consisting of a polyester polyol of which the average number of hydroxy groups per molecule and the molecular weight are specified.
The average number of hydroxy groups contained in the polyol (A) is 2.2 or more, preferably 2.3 or more, and more preferably 2.5 or more. The upper limit is preferably 3.5, more preferably 3.0.
In addition, the molecular weight of the polyol (A) is less than 500, preferably 260 to 470, more preferably 300 to 450.

The hydroxyl value of the polyol (A) is preferably 300 to 600 mg KOH / g, more preferably 400 to 500 mg KOH / g.
The number of ester bonds contained in the polyol (A) is not particularly limited, but is preferably 2 to 4 and more preferably 2 to 3.

The above-mentioned polyol (B) is a polyol which does not have an ester bond, is composed of a compound having an aromatic hydrocarbon group or an alicyclic hydrocarbon group and two or more hydroxy groups and having a molecular weight of less than 450. . The polyol (B) may be either an aromatic polyol or an alicyclic polyol, and the polyol (B) contained in the polyol composition of the present invention may be only one or two or more. May be

When the said polyol (B) is an aromatic polyol, the aromatic hydrocarbon group contained in this aromatic polyol and its number are not specifically limited.
Examples of the aromatic hydrocarbon group include phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, 2-azulenyl group, 1-pyrenyl group, 2-triphenyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group and the like can be mentioned.

As said aromatic polyol,
(B1) An aromatic compound having two hydroxy groups directly bonded to a carbon atom constituting an aromatic ring, such as an aromatic diol exemplified as a polyhydric alcohol which is a raw material for producing the above-mentioned polyol (A) ) Aromatic polyether polyols obtained by addition of alkylene oxide (b2) Addition of (poly) alkylene oxide to an aromatic compound having three or more hydroxy groups directly bonded to carbon atoms constituting the aromatic ring The aromatic polyether polyol etc. which were obtained by adding (poly) alkylene oxide to the aromatic polyether polyol (b3) aromatic polyhydric amine obtained by this method are mentioned.
In addition, ethylene oxide, a propylene oxide, a butene oxide etc. are mentioned as said (poly) alkylene oxide.

The aromatic polyol is preferably an aromatic polyether polyol (b1), and more preferably a compound represented by the following general formula (1).

As a compound represented by the said General formula (1), the compound whose m1 and m2 are integers greater than or equal to 1, n1 is 0, and n2 and n3 are 1 is preferable. As such a compound, a compound represented by the following general formula (1-1) can be used.

Examples of the compound represented by the above general formula (1-1) include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene- (2.3) -2 Adducts of 2,2-bis (4-hydroxyphenyl) propane such as 2-bis (4-hydroxyphenyl) propane; polyoxypropylene- (2.0) -2,2-bis (4-) Polyoxypropylene adducts of 2,2-bis (4-hydroxyphenyl) propane such as hydroxyphenyl) propane and polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane; Propylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2 2-Bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4 And -hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane and the like.

When the polyol (B) is an alicyclic polyol, the alicyclic hydrocarbon group contained in the alicyclic polyol and the number thereof are not particularly limited.
Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group and 2-indeno group, and decahydronaphthyl group And an adamantyl group.

Examples of the alicyclic polyol include alicyclic diols, alicyclic triols and alicyclic tetraols. Among these, an alicyclic diol is preferable, and a compound represented by the following general formula (2) is more preferable.

(Wherein, R ⁵ , R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and p 1, p 2, p 3 and p 4 are each independently of each other) And q 1 and q 2 are each independently an integer of 0 to 6.)

As an alicyclic diol represented by the said General formula (2), 6-membered ring diol represented by following General formula (2-1) whose q1 is 3, and q1 and q2 are 3. The six-membered ring diol represented by the following general formula (2-2) is preferable.

As the 6-membered ring diol represented by the above general formula (2-1), a compound in which p1 and p2 are 0 and a compound in which p1 and p2 are 1 are preferable, and 1,2-cyclohexanediol, 1, 3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like can be used.
As the 6-membered ring diol represented by the above general formula (2-2), compounds in which p1 and p2 are 0 and p3 is 1 and compounds in which p1, p2 and p3 are 1 are preferable, and 2 And 2-bis (4-hydroxycyclohexyl) propane can be used.
In the present invention, as the alicyclic diol, a 5-membered ring diol having q1 and q2 of 2, for example, 1,2-cyclopentadimethanol, 1,3-cyclopentadimethanol etc. can also be used. .

Examples of the alicyclic triol include cyclohexanetriol, 1,2,4-cyclohexanetrimethanol, 1,3,5-cyclohexanetrimethanol and the like.
Examples of the alicyclic tetraol include 1,2,4,5-cyclohexanetetramethanol and the like.

The polyol (B) according to the present invention has a self-repairing function and facilitates a film having a durometer hardness of 60 or more by a coating composition having a specific range of isocyanate index in combination with the polyol (A) and polyisocyanate. The polyol composition of the present invention comprises a polyol (B) of specified molecular weight.
The molecular weight of the polyol (B) is less than 450, preferably 100 to 430, more preferably 120 to 400.

The average number of hydroxy groups contained in the polyol (B) is preferably 2 to 3, and more preferably 2.
The hydroxyl value of the polyol (B) is preferably 260 to 1250 mg KOH / g, more preferably 280 to 935 mg KOH / g.

The content ratio of the polyols (A) and (B) contained in the polyol composition of the present invention is not particularly limited, but they are used in combination with a polyisocyanate to make a self-repairing with a coating composition having a specific range of isocyanate index. Preferably, 55 to 93% by mass and 7 to 45% by mass, when the total of the both is 100% by mass, because they have a function and a durometer hardness of 60 or more can be easily obtained. More preferably, it is 58 to 92% by mass and 8 to 42% by mass, still more preferably 60 to 90% by mass and 10 to 40% by mass.

In the polyol composition of the present invention, the average number of hydroxy groups derived from the hydroxy group contained in the polyol (A) and the hydroxy group contained in the polyol (B) is preferably 2.2 to 3.5, more preferably Is 2.5 to 3.0.
The average hydroxyl value of the polyol (A) and the polyol (B) is preferably 350 to 600 mg KOH / g, more preferably 400 to 550 mg KOH / g.

The polyol composition of the present invention may further contain other polyols as described above. Examples of other polyols include polyester polyols other than the polyol (A), and polyols other than the polyol (B) such as polycarbonate polyol, polydiene polyol, acrylic polyol and silicone polyol.
When the polyol composition of the present invention contains another polyol, the upper limit of the content ratio is preferably 30 parts by mass, more preferably 100 parts by mass of the total of the polyols (A) and (B). Is 20 parts by mass.

In addition, the polyol composition of the present invention is an additive such as a foam stabilizer, a colorant, a plasticizer, a filler, an ultraviolet absorber, a flame retardant, a coupling agent, an antioxidant, an antiaging agent, a fragrance, a dispersion medium, etc. Can be contained.

The coating composition of the present invention contains the polyol composition of the present invention and a polyisocyanate, and the total mole of isocyanate groups derived from the polyisocyanate relative to the total molar amount of hydroxy groups derived from the polyol composition It is characterized in that the ratio of the amounts is 0.8 to 1.1.

The above polyisocyanate is not particularly limited as long as it has two or more isocyanate groups, and is an aromatic compound (hereinafter referred to as "aromatic isocyanate"), an aliphatic compound (hereinafter referred to as "aliphatic isocyanate"), Any of alicyclic compounds (hereinafter referred to as "alicyclic isocyanate") may be used. Moreover, although the number of polyisocyanates contained in the coating composition of the present invention may be only one or two or more, the average number of isocyanate groups per molecule is preferably 3.0 to It is 4.0, more preferably 3.0 to 3.5.

As the above aromatic isocyanate, diphenylmethane diisocyanate (MDI) such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, etc .; crude diphenylmethane diisocyanate; polynuclear polyphenylene polymethyl polyisocyanate (polymeric MDI); tolylene diisocyanate (TDI) such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate; naphthalene diisocyanate (NDI) such as 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate; 1,5- Tetrahydronaphthalene diisocyanate; 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4 Phenylene diisocyanate (PDI) such as phenylene diisocyanate; xylene diisocyanate (XDI); tetramethyl xylylene diisocyanate (TMXDI); tolidine diisocyanate (TODI); 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4, 6-triisopropylphenyl-1,3-diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxymethane -4,4'-diphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate and the like may be mentioned, and modified compounds thereof may be used.

Examples of the aliphatic isocyanate include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHMDI), dodecamethylene diisocyanate, lysine diisocyanate (LDI), lysine triisocyanate (LTI), etc. And modified compounds thereof.
Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate, hydrogenated XDI (H ₆ XDI), hydrogenated MDI (H ₁₂ MDI), norbornene diisocyanate (NBDI) etc. are mentioned and these modified compounds may be sufficient.

When the above polyisocyanate is a modifying compound, a compound having allophanate bond, biuret bond, urethane bond, urea bond, etc., isocyanurate modified body, carbodiimide modified body, uretonimine modified body, uretdione modified body, acylated urea modified body, Blocked products (phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite, sodium bisulfite, etc.) .

As the above-mentioned polyisocyanate, it is preferable to include a polyisocyanate having an allophanate bond, since a sufficient self-repairing function is exerted when the surface of the film is scratched.

When the above polyisocyanate contains two or more kinds of polyisocyanate, the content ratio (average value) of the isocyanate group derived from the above polyisocyanate is preferably 15 to 25% by mass, more preferably 18 to 24% by mass. is there.

The content of the polyisocyanate contained in the coating composition of the present invention is not particularly limited, but the content of the isocyanate group derived from the above polyisocyanate relative to the total molar amount or the average molar amount of hydroxy groups derived from the above polyol composition The ratio of the total molar amount or the average molar amount, that is, the isocyanate index (NCO / OH equivalent ratio) is determined. In the present invention, this isocyanate index is 0.8 to 1.1, preferably 0.9 to 1.05.

The coating composition of the present invention further comprises dyes, pigments, plasticizers, catalysts, fungicides, antifoaming agents, antifoaming agents, leveling agents, pigment dispersants, antisettling agents, anti-sagging agents, thickeners, matting agents, Additives such as light stabilizers, ultraviolet light absorbers and mold release agents can be contained.

The coating composition of the present invention can be produced by mixing the polyol composition of the present invention and a polyisocyanate in an amount corresponding to a predetermined isocyanate index.

The coating composition of the present invention is suitable for application to a substrate including an inorganic material such as metal or ceramic, or an organic material such as plastic or rubber. As a method of applying to an object to be coated, a spray coating method, a roll coating method, a brush coating method, a spin coating method, a bar coating method, a reverse coating method, a slit coating method, a dipping method, a kiss coating method, a reverse kiss coating method, an air knife A coating method, a curtain coating method, a rod coating method, a gravure coating method, a die coating method or the like can be applied.

In the present invention, after the coating composition is applied to a substrate, the resulting coating is subjected to urethanation reaction in an atmosphere such as air at a temperature in the range of 20 ° C. to 100 ° C. for at least 1 hour. By leaving at least 1 hour at a temperature in the range of 20 ° C. to 100 ° C., the urethanization reaction can be accelerated and completed to obtain a film having a self-repairing function. The thickness of the coating for obtaining a coating having a self-repairing function is at least 10 μm.

The durometer hardness of the film obtained using the paint composition of the present invention is preferably 60 or more, more preferably 65 or more.
In addition, when the surface of the film is scratched, the self-repairing function is exhibited by leaving it in an atmosphere of less than 50 ° C., for example, 20 ° C. to 45 ° C. for at least one hour.
Accordingly, the coating composition of the present invention is suitable for the production of an article coated and having a film on the surface thereof, for example, a vehicle, a railway vehicle, an aircraft, a ship, a spacecraft, a submersible, a snowmobile, a mountain area or It is suitable for forming a film on the surface of an interior part or exterior part such as a gondola of an amusement park, a play vehicle part, etc., an electronic device, a home appliance, a boiler pipe, an exhaust pipe, a housing material, a door material, a handrail or the like.

The coating composition of the present invention can also be used as an additive (coating composition for paint) which is conventionally blended in a known coating and gives the same effect.
The additive amount of the additive comprising the coating composition of the present invention to the coating is not particularly limited, but the self-repairing function is surely exerted when the surface of the film is scratched. The solid content is preferably 0.1 to 40 parts by mass, more preferably 0.2 to 30 parts by mass, with respect to 100 parts by mass of the solid content of the paint.

The base resin or base rubber contained in the paint which can use the above additive is not particularly limited, and alkyd resin, acrylic resin, acrylic urethane resin, melamine resin, urethane resin, epoxy resin, coumarone resin, urea resin, phenol resin, Examples include vinyl chloride resin, silicone resin, fluorine resin, nylon resin, styrene butadiene rubber, acrylonitrile butadiene rubber, petroleum resin, rosin, drying oil, boiled oil, acetyl cellulose, nitrocellulose and the like.

1. Production of Polyol Composition Experimental Example 1-1
After replacing the inside of the four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 111 parts by mass of adipic acid, 36 parts by mass of 1,4-butanediol, 3-methyl-1 48 parts by mass of 5-pentanediol and 105 parts by mass of trimethylolpropane were charged, and the temperature was raised to 140 ° C. while introducing nitrogen gas. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 200 ° C. At that time, heating was continued until the acid value of the reaction product became 1.0 mg KOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 352, an average number of hydroxy groups of 3, a hydroxyl value of 478.0 mg KOH / g, and an acid value of 0.7 mg KOH / g (hereinafter referred to as "polol (A1)") was obtained.
Next, this polyol (A1) and 1,4-cyclohexanedimethanol (B1) are blended at a mass ratio of 8: 2 to obtain a polyol composition (hereinafter referred to as "polyol composition (S1)"). The
The average hydroxy group number of the obtained polyol composition (S1) is 2.8, the average hydroxyl value is 538 mg KOH / g, and the average molecular weight is 311 (see Table 1).

Experimental Example 1-2
The polyol (A1) and 1,4-cyclohexanedimethanol (B1) were blended at a mass ratio of 7: 3 to obtain a polyol composition (hereinafter referred to as "polyol composition (S2)").
The average hydroxy group number of the obtained polyol composition (S2) is 2.5, the average hydroxyl value is 568 mg KOH / g, and the average molecular weight is 290 (see Table 1).

Experimental Example 1-3
After replacing the inside of the four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 138 parts by mass of sebacic acid, 27 parts by mass of 1,3-propanediol, 3-methyl-1 42 parts by mass of 5, 5-pentanediol and 93 parts by mass of trimethylolpropane were charged, and the temperature was raised to 140 ° C. while introducing nitrogen gas. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 200 ° C. At that time, heating was continued until the acid value of the reaction product became 1 mgKOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 402, an average number of hydroxy groups of 3, a hydroxyl value of 419.0 mg KOH / g, and an acid value of 0.7 mg KOH / g (hereinafter referred to as "polol (A2)") was obtained.
Next, this polyol (A2) and 1,4-cyclohexanedimethanol (B1) are blended at a mass ratio of 8: 2, to obtain a polyol composition (hereinafter referred to as "polyol composition (S3)"). The
The average hydroxy group number of the obtained polyol composition (S3) is 2.8, the average hydroxyl value is 491 mg KOH / g, and the average molecular weight is 350 (see Table 1).

Experimental Example 1-4
The polyol (A2) and 1,4-cyclohexanedimethanol (B1) were blended at a mass ratio of 7: 3 to obtain a polyol composition (hereinafter referred to as "polyol composition (S4)").
The average hydroxy group number of the obtained polyol composition (S4) is 2.5, the average hydroxyl value is 527 mg KOH / g, and the average molecular weight is 324 (see Table 1).

Experimental Example 1-5
The polyol (A2) and a propylene oxide adduct of bisphenol A (B2) ("BPX-11" manufactured by ADEKA) are blended at a mass ratio of 6: 4, and a polyol composition (hereinafter referred to as "polyol composition S5) say ").
The average hydroxyl group number of the obtained polyol composition (S5) is 2.6, the average hydroxyl value is 367 mg KOH / g, and the average molecular weight is 383 (see Table 1).

Experimental Example 1-6
After replacing the inside of the four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 105 parts by mass of adipic acid, 45 parts by mass of 3-methyl-1,5-pentanediol and 150 parts by mass of methylolpropane were charged, and the temperature was raised to 140 ° C. while introducing nitrogen gas. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 200 ° C. At that time, heating was continued until the acid value of the reaction product became 1 mgKOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 374, an average number of hydroxy groups of 3.5, a hydroxyl value of 524.0 mg KOH / g, and an acid value of 0.7 mg KOH / g (hereinafter referred to as "polol (A3)") was obtained.
Next, this polyol (A3) and 1,4-cyclohexanedimethanol (B1) are blended at a mass ratio of 8: 2 to obtain a polyol composition (hereinafter referred to as "polyol composition (S6)"). The
The average hydroxy group number of the obtained polyol composition (S6) is 3.2, the average hydroxyl value is 575 mg KOH / g, and the average molecular weight is 328 (see Table 1).

Experimental Example 1-7
After replacing the inside of the four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 120 parts by mass of adipic acid, 72 parts by mass of 1,4-butanediol and 108 parts by mass of trimethylolpropane Parts were charged and the temperature was raised to 150.degree. C. while introducing nitrogen gas. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 180 ° C. At that time, heating was continued until the acid value of the reaction product became 1 mgKOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 338, an average number of hydroxy groups of 3, a hydroxyl value of 497.0 mg KOH / g, and an acid value of 0.8 mg KOH / g (hereinafter referred to as "polol (A4)") was obtained.
Next, this polyol (A4) and 1,4-cyclohexanedimethanol (B1) are blended at a mass ratio of 8: 2 to obtain a polyol composition (hereinafter referred to as "polyol composition (S7)"). The
The average hydroxy group number of the obtained polyol composition (S7) is 2.8, the average hydroxyl value is 554 mg KOH / g, and the average molecular weight is 300 (see Table 1).

Experimental Example 1-8
The polyol (A4) and the propylene oxide adduct of bisphenol A (B2) were blended at a mass ratio of 9: 1 to obtain a polyol composition (hereinafter referred to as "polyol composition (S8)").
The average hydroxyl group number of the obtained polyol composition (S8) is 2.9, the average hydroxyl value is 479 mg KOH / g, and the average molecular weight is 340 (see Table 1).

Experimental Example 1-9
The polyol (A4) and the propylene oxide adduct of bisphenol A (B2) were blended at a mass ratio of 8: 2, to obtain a polyol composition (hereinafter referred to as "polyol composition (S9)").
The average hydroxy group number of the obtained polyol composition (S9) is 2.8, the average hydroxyl value is 461 mg KOH / g, and the average molecular weight is 342 (see Table 1).

Experimental Example 1-10
The polyol (A4) and the propylene oxide adduct of bisphenol A (B2) were blended at a mass ratio of 7: 3 to obtain a polyol composition (hereinafter referred to as "polyol composition (S10)").
The average hydroxy group number of the obtained polyol composition (S10) is 2.5, the average hydroxyl value is 443 mg KOH / g, and the average molecular weight is 343 (see Table 1).

Experimental Example 1-11
After replacing the inside of the four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 117 parts by mass of adipic acid, 75 parts by mass of 1,4-butanediol, 3-methyl-1 51 parts by mass of 5, 5-pentanediol and 57 parts by mass of trimethylolpropane were charged, and the temperature was raised to 140 ° C. while introducing nitrogen gas. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 200 ° C. At that time, heating was continued until the acid value of the reaction product became 1 mgKOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 331, an average number of hydroxy groups of 2.5, a hydroxyl value of 424.0 mg KOH / g, and an acid value of 0.6 mg KOH / g (hereinafter referred to as "polol (A5)") was obtained.
Next, this polyol (A5) and the propylene oxide adduct of bisphenol A (B2) are blended at a mass ratio of 8: 2, and a polyol composition (hereinafter referred to as "polyol composition (S11)") is obtained. Obtained.
The average hydroxyl group number of the obtained polyol composition (S11) is 2.4, the average hydroxyl value is 403 mg KOH / g, and the average molecular weight is 335 (see Table 1).

Experimental Example 1-12
The polyol (A5) and the propylene oxide adduct of bisphenol A (B2) were blended at a mass ratio of 7: 3 to obtain a polyol composition (hereinafter referred to as "polyol composition (S12)").
The average hydroxy group number of the obtained polyol composition (S12) is 2.4, the average hydroxyl value is 392 mg KOH / g, and the average molecular weight is 338 (see Table 1).

Experimental Example 1-13
After replacing the inside of the four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 147 parts by mass of adipic acid, 93 parts by mass of 1,4-butanediol and 3-methyl-1 60 parts by mass of 5, 5-pentanediol was charged, and the temperature was raised to 140 ° C. while introducing nitrogen gas. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 200 ° C. At that time, heating was continued until the acid value of the reaction product became 1 mgKOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 519, an average number of hydroxy groups of 2, a hydroxyl value of 216.0 mg KOH / g, and an acid value of 0.7 mg KOH / g (hereinafter referred to as "polol (A6)") was obtained.
Next, this polyol (A6) and the propylene oxide adduct of bisphenol A (B2) are blended at a mass ratio of 8: 2, and a polyol composition (hereinafter referred to as "polyol composition (S13)") is obtained. Obtained.
The average hydroxy group number of the obtained polyol composition (S13) is 2.0, the average hydroxyl value is 236 mg KOH / g, and the average molecular weight is 486 (see Table 1).

Experimental Example 1-14
The polyol (A6) and the propylene oxide adduct of bisphenol A (B2) were blended at a mass ratio of 7: 3 to obtain a polyol composition (hereinafter referred to as "polyol composition (S14)").
The average hydroxyl group number of the obtained polyol composition (S14) is 2.0, the average hydroxyl value is 246 mg KOH / g, and the average molecular weight is 470 (see Table 1).

Experimental Example 1-15
After replacing the inside of a four-neck Kolben equipped with a stirrer, a water test tube, a thermometer and a nitrogen blowing line with nitrogen gas, 126 parts by mass of adipic acid and 174 parts by mass of trimethylolpropane are charged, and nitrogen gas is introduced The temperature was raised to 140 ° C. At this temperature, the esterification reaction was started while distilling out water, and the temperature was raised to 220 ° C. to continue the reaction. Thereafter, the reaction solution was cooled to 80 ° C., 0.03 parts by mass of stannous octoate was added, and the temperature was raised to 200 ° C. At that time, heating was continued until the acid value of the reaction product became 1 mgKOH / g or less while setting the inside of the Kolben under reduced pressure conditions and further distilling off water. As a result, a polyester polyol having a molecular weight of 623, an average number of hydroxy groups of 5, a hydroxyl value of 450.0 mg KOH / g, and an acid value of 0.7 mg KOH / g (hereinafter referred to as "polol (A7)") was obtained.
Next, this polyol (A7) and the propylene oxide adduct of bisphenol A (B2) are blended at a mass ratio of 8: 2, and a polyol composition (hereinafter referred to as "polyol composition (S15)") is obtained. Obtained.
The average hydroxyl group number of the obtained polyol composition (S15) is 4.4, the average hydroxyl value is 424 mg KOH / g, and the average molecular weight is 569 (see Table 1).

Experimental Example 1-16
The polyol (A7) and the propylene oxide adduct of bisphenol A (B2) were blended at a mass ratio of 7: 3 to obtain a polyol composition (hereinafter referred to as "polyol composition (S16)").
The average hydroxy group number of the obtained polyol composition (S16) is 4.1, the average hydroxyl value is 410 mg KOH / g, and the average molecular weight is 543 (see Table 1).

Experimental Example 1-17
The polyol (A2) and 1,4-butanediol (B3) were blended at a mass ratio of 85:15 to obtain a polyol composition (hereinafter referred to as "polyol composition (S17)").
The average hydroxyl group number of the obtained polyol composition (S17) is 2.9, the average hydroxyl value is 543 mg KOH / g, and the average molecular weight is 355 (see Table 1).

2. Production and Evaluation of Coating Composition The coating composition was produced using the polyol composition obtained in the above-mentioned Experimental Examples 1-1 to 1-17 and the following polyisocyanate.
(C1) "Duranate TSA-100" (trade name) manufactured by Asahi Kasei Corporation
Hexamethylene diisocyanate-based polyisocyanate having an isocyanurate structure and containing allophanate group (C2) "Duranate TPA-100" (trade name) manufactured by Asahi Kasei Corporation
Hexamethylene diisocyanate-based polyisocyanate which has isocyanurate structure and does not contain allophanate group (C3) "Duranate 24A-100" manufactured by Asahi Kasei (trade name)
Hexamethylene diisocyanate-based polyisocyanate which has biuret structure and does not contain allophanate group (C4) "Duranate TSE-100" manufactured by Asahi Kasei Co., Ltd. (trade name)
Hexamethylene diisocyanate-based polyisocyanate containing allophanate group

Experimental Example 2-1
A paint composition containing 10 parts by mass of the polyol composition (S1) and 19.5 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T1)" Got).
Next, the coating composition (T1) was applied to the surface of a steel plate using an applicator, and the thickness of the film after drying was 25 μm (for self-repair function evaluation and pencil hardness measurement) or 10 mm (urethane hardness measurement) It applied so that it might become), and it left still at 25 degreeC in air | atmosphere for 1 hour. Thereafter, the film was allowed to stand at 85 ° C. for 16 hours and further at 25 ° C. for 24 hours to obtain a polyurethane resin film.

The self-repairing function and hardness of the obtained polyurethane resin film were evaluated by the following method, and the results are shown in Table 2.
(1) Self-healing function With the tip of a brass brush in contact with the surface of a 25 μm thick polyurethane resin film, a 50 mm length is reciprocated 10 times at a moving speed of 100 mm per second to scratch the film. I put it. Then, it was allowed to stand in a temperature-controlled room adjusted to 25 ° C., and after 1 hour, it was confirmed whether or not the wound was recovered and smoothed. If the wound did not recover, it was allowed to stand in a temperature-controlled room adjusted to 40 ° C., and after 1 hour it was checked whether the wound recovered and became smooth.
○: The wound was recovered ×: The wound was not recovered (2) Hardness The pencil hardness of the polyurethane resin film with a thickness of 25 μm was measured using a pencil hardness tester manufactured by Kotec in accordance with JIS K5600-5-4. It was measured. The load is 750 g. In addition, the durometer hardness (type D) of a polyurethane resin film having a thickness of 10 mm was recorded as a measurement value after 15 seconds using a durometer manufactured by ASKER in accordance with JIS K6253-3.

Experimental Example 2-2
A paint composition containing 10 parts by mass of the polyol composition (S2) and 20.6 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T2)" Got). And various evaluation was performed using this coating composition (T2). The results are shown in Table 2.

Experimental Example 2-3
10 parts by mass of the polyol composition (S3) and 17.8 parts by mass of the polyisocyanate (C1) are mixed, and a coating composition having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T3)" Got). And various evaluation was performed using this coating composition (T3). The results are shown in Table 2.

Experimental Example 2-4
A paint composition containing 10 parts by mass of the polyol composition (S4) and 19.1 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T4)" Got). And various evaluation was performed using this coating composition (T4). The results are shown in Table 2.

Experimental Example 2-5
A paint composition containing 10 parts by mass of the polyol composition (S5) and 13.3 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "paint composition (T5)" Got). And various evaluation was performed using this coating composition (T5). The results are shown in Table 2.

Experimental Example 2-6
A paint composition containing 10 parts by mass of the polyol composition (S6) and 20.9 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T6)" Got). And various evaluation was performed using this coating composition (T6). The results are shown in Table 2.

Experimental Example 2-7
A paint composition containing 10 parts by mass of the polyol composition (S7) and 20.1 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T7)" Got). And various evaluation was performed using this coating composition (T7). The results are shown in Table 2.

Experimental Example 2-8
A paint composition containing 10 parts by mass of the polyol composition (S8) and 17.4 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T8)" Got). And various evaluation was performed using this paint composition (T8). The results are shown in Table 2.

Experimental Example 2-9
10 parts by mass of the above polyol composition (S9) and 16.8 parts by mass of the above polyisocyanate (C1) are mixed, and a coating composition having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T9)" Got). And various evaluation was performed using this paint composition (T9). The results are shown in Table 2.

Experimental Example 2-10
10 parts by mass of the polyol composition (S9) and 13.4 parts by mass of the polyisocyanate (C1) are mixed, and a coating composition having an isocyanate index of 0.8 (hereinafter referred to as "coating composition (T10)" Got). And various evaluation was performed using this paint composition (T10). The results are shown in Table 2.

Experimental Example 2-11
A paint composition containing 10 parts by mass of the polyol composition (S9) and 18.4 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.1 (hereinafter referred to as "coating composition (T11)" Got). And various evaluation was performed using this coating composition (T11). The results are shown in Table 2.

Experimental Example 2-12
A paint composition containing 10 parts by mass of the polyol composition (S9) and 14.9 parts by mass of the polyisocyanate (C2) and having an isocyanate index of 1.0 (hereinafter referred to as "paint composition (T12)" Got). And various evaluation was performed using this paint composition (T12). The results are shown in Table 2.

Experimental Example 2-13
10 parts by mass of the above-mentioned polyol composition (S9), 6.8 parts by mass of the above-mentioned polyisocyanate (C2), and 15.8 parts by mass of the above-mentioned polyisocyanate (C4) An article (hereinafter, referred to as "coating composition (T13)") was obtained. And various evaluation was performed using this coating composition (T13). The results are shown in Table 2.

Experimental Example 2-14
A paint composition containing 10 parts by mass of the polyol composition (S9) and 14.7 parts by mass of the polyisocyanate (C3) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T14)" Got). And various evaluation was performed using this coating composition (T14). The results are shown in Table 2.

Experimental Example 2-15
A paint composition containing 10 parts by mass of the polyol composition (S10) and 16.0 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T15)" Got). And various evaluation was performed using this coating composition (T15). The results are shown in Table 2.

Experimental Example 2-16
A paint composition containing 10 parts by mass of the polyol composition (S11) and 14.6 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "paint composition (T16)" Got). And various evaluation was performed using this coating composition (T16). The results are shown in Table 2.

Experimental Example 2-17
A paint composition containing 10 parts by mass of the polyol composition (S12) and 14.2 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T17)" Got). And various evaluation was performed using this coating composition (T17). The results are shown in Table 2.

Experimental Example 2-18
A paint composition containing 10 parts by mass of the polyol composition (S13) and 8.6 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T18)" Got). And various evaluation was performed using this coating composition (T18). The results are shown in Table 3.

Experimental Example 2-19
A paint composition containing 10 parts by mass of the polyol composition (S14) and 8.9 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T19)" Got). And various evaluation was performed using this paint composition (T19). The results are shown in Table 3.

Experimental Example 2-20
A paint composition containing 10 parts by mass of the polyol composition (S15) and 15.4 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T20)" Got). And various evaluation was performed using this paint composition (T20). The results are shown in Table 3.

Experimental Example 2-21
A paint composition containing 10 parts by mass of the polyol composition (S16) and 14.9 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T21)" Got). And various evaluation was performed using this coating composition (T21). The results are shown in Table 3.

Experimental Example 2-22
A paint composition containing 10 parts by mass of the polyol composition (S9) and 11.7 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 0.7 (hereinafter referred to as "coating composition (T22)" Got). And various evaluation was performed using this coating composition (T22). The results are shown in Table 3.

Experimental Example 2-23
A paint composition containing 10 parts by mass of the polyol composition (S9) and 20.1 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.2 (hereinafter referred to as "coating composition (T23)" Got). And various evaluation was performed using this coating composition (T23). The results are shown in Table 3.

Experimental Example 2-24
A paint composition containing 10 parts by mass of the polyol composition (S17) and 19.0 parts by mass of the polyisocyanate (C1) and having an isocyanate index of 1.0 (hereinafter referred to as "coating composition (T24)" Got). And various evaluation was performed using this paint composition (T24). The results are shown in Table 3.

The following were found from Tables 2 and 3. Experimental Examples 2-18 to 2-21 are examples in which a coating composition is formed using a polyol composition containing a polyol (A6) or (A7) having a molecular weight of 500 or more, and the obtained film has a self-repairing function. It did not demonstrate. Experimental Example 2-22 is an example where the isocyanate index in the coating composition is low outside the scope of the present invention, and the obtained film exhibited a self-repairing function, but a sufficient hardness was not obtained. Experimental Example 2-23 is an example in which the isocyanate index in the paint composition is high outside the scope of the present invention, and the obtained film did not exhibit a self-repairing function. Further, in Experimental Example 2-24, a polyol composition containing 1,4-butanediol, which is a polyol not containing an aromatic hydrocarbon group and an alicyclic hydrocarbon group, in place of the polyol (B) according to the present invention And the obtained film did not exhibit a self-repairing function. On the other hand, Experimental Examples 2-1 to 2-17 are examples included in the present invention, and a film having a self-repairing function and having a durometer hardness of 60 or more could be obtained.

The polyol composition of the present invention is suitable for preparation of a coating composition having a self-repairing function and giving a film having a durometer hardness of 60 or more.
The coating composition of the present invention has a self-repairing function and provides a film having a durometer hardness of 60 or more, so that it can be used as a vehicle, railway vehicle, aircraft, ship, spacecraft, submersible, snowmobile, mountain or amusement park. It is suitable for coating on interior parts or exterior parts such as gondolas and play vehicle parts, electronic equipment, home appliances, boiler piping, exhaust pipes, housing materials, door materials, handrails and the like. Further, the coating composition of the present invention may be alkyd resin, acrylic resin, acrylic urethane resin, melamine resin, urethane resin, epoxy resin, coumarone resin, urea resin, phenol resin, vinyl chloride resin, silicone resin, fluorine resin, nylon resin It can be used as an additive (additive composition for paint) to a base resin such as vinyl chloride resin, styrene butadiene resin, nitrile butadiene resin, petroleum resin, rosin and the like.

Claims

(A) A polyol comprising an ester bond and two or more hydroxy groups and having a molecular weight of less than 500, and having an average number of hydroxy groups per molecule of 2.2 or more,
(B) It is characterized by containing a polyol which does not have an ester bond, has an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and two or more hydroxy groups and has a molecular weight of less than 450. And polyol composition.
The polyol composition according to claim 1, wherein the polyol (A) is a condensate of a polyhydric alcohol and a dibasic acid.
The polyol (A) is an aliphatic compound comprising a condensate of a first polyhydric alcohol having two hydroxy groups, a second polyhydric alcohol having three or more hydroxy groups, and a dibasic acid. The polyol composition according to claim 2.
The polyol composition according to any one of claims 1 to 3, wherein the polyol (B) is a diol.
The polyol composition according to claim 4, wherein the diol is at least one selected from a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

(Wherein, R 1 and R 2 are each independently an aliphatic hydrocarbon group having 2 to 4 carbon atoms, and R 3 and R 4 are each independently having 1 to 4 carbon atoms And m1 and m2 are each independently an integer of 0 to 3, and n1, n2 and n3 are each independently 0 or 1).

(Wherein, R 5 , R 6 and R 7 are each independently an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and p 1, p 2, p 3 and p 4 are each independently of each other) And q 1 and q 2 are each independently an integer of 0 to 6.)
The content ratio of the above-mentioned polyol (A) and the above-mentioned polyol (B) is 55-93 mass% and 7-45 mass%, respectively, when the sum total of both is 100 mass%. Polyol composition according to any one of the preceding claims.
The polyol composition according to any one of claims 1 to 6, wherein the average hydroxyl group number of the polyol composition is 2.2 to 3.5, and the average hydroxyl value is 350 to 600 mg KOH / g.
A polyol composition according to any one of claims 1 to 7 and a polyisocyanate.
A coating composition characterized in that a ratio of a total molar amount of isocyanate groups derived from the polyisocyanate to a total molar amount of hydroxy groups derived from the polyol composition is 0.8 to 1.1.
The coating composition according to claim 8, wherein the average number of isocyanate groups per molecule of the polyisocyanate is 3.0 to 4.0.
The paint composition according to claim 8 or 9, wherein the polyisocyanate has an allophanate bond.
The paint composition according to any one of claims 8 to 10, wherein the obtained film has a self-repairing function.