JP2018012769A - Coating Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition that can form a coated film having excellent solvent resistance and sunscreen resistance.SOLUTION: A coating composition contains (A) a polycarbonate diol composition that contains 5-50 mass% of polyoxyethylene structures with the number of repetitions of 9-50, and 50-95 mass% of polycarbonate structures represented by formula 2, and has a number average molecular weight of 300-10000, (B) a polyol other than (A), and (C) an isocyanate compound. Based on the total of 100 mass% of (A) and (B), the (A) content is 40-100 mass% and the (B) content is 0-60 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a coating composition.

Conventionally, polyurethane resins are used in a wide range of areas such as synthetic leather, artificial leather, adhesives, furniture paints, and automobile paints. Polyols, polyesters, and polycarbonates having hydroxy groups as polyol components that react with isocyanates. Has been used. However, in recent years, demands for resin resistance such as heat resistance, weather resistance, hydrolysis resistance, solvent resistance and sunscreen resistance are increasing.
In general, it is known that a polyurethane resin using polycarbonate diol as a polyol component is more excellent in chemical resistance and sun resistance than a polyurethane resin using a polyether or polyester having a hydroxy group. For example, Patent Document 1 proposes a coating composition using polycarbonate diol as a polyol component.

JP 2012-219238 A

However, polyurethane resins using polycarbonate diol as disclosed in Patent Document 1 have room for improvement in applications such as automotive paints, which have strict requirements for physical properties such as solvent resistance and sun resistance. is there.
Then, an object of this invention is to provide the coating composition which can form the coating film which is excellent in solvent resistance and sunscreen resistance.

As a result of intensive studies in order to solve the above-mentioned problems of the prior art, the present inventor has obtained a solvent resistance and a sun resistance by using a coating composition containing a polycarbonate diol having a specific structure and an isocyanate compound. The present inventors have found that a coating film having excellent properties can be obtained, and have made the present invention.
That is, the configuration of the present invention is as follows.

[1]
(A) The molecular chain contains a polyoxyethylene structure represented by (Formula 1) and a polycarbonate structure represented by (Formula 2),
The terminal structure of the polyoxyethylene structure is a structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, or a structure in which both terminals are bonded to a carbonate group,
Both ends are hydroxyl groups,
A polycarbonate diol composition comprising a polycarbonate diol,
The whole composition contains 5 to 50% by mass of the polyoxyethylene structure represented by (Formula 1), 50 to 95% by mass of the polycarbonate structure represented by (Formula 2), and has a number average molecular weight of 300 to A composition that is 10,000;
(B) a polyol component other than (A) above; and
(C) an isocyanate compound;
The coating composition which contains 40-100 mass% of said (A), and 0-60 mass% of said (B) with respect to a total of 100 mass% of said (A) and said (B).
(In formula, m represents the number of 9-50.)
(In the formula, R may be the same or different and each represents an optionally substituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 2 to 15 carbon atoms. And n represents a number from 1 to 50.)
[2]
The polycarbonate diol composition comprises, in the whole composition, 5 to 30% by mass of the polyoxyethylene structure represented by (Formula 1) and 70 to 95% by mass of the polycarbonate structure represented by (Formula 2). The coating composition according to [1], comprising:
[3]
The coating composition according to [1] or [2], wherein the polyoxyethylene structure is a polyoxyethylene structure represented by (Formula 3).
(In the formula, l represents a number of 9 to 30.)

  According to the coating composition of this invention, it has the effect that the coating film excellent in solvent resistance and sunscreen resistance can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following description, It can implement by changing variously within the range of the summary.

<Coating composition>
The coating composition of this embodiment is
(A) The molecular chain contains a polyoxyethylene structure represented by (Formula 1) and a polycarbonate structure represented by (Formula 2),
The terminal structure of the polyoxyethylene structure is a structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, or a structure in which both terminals are bonded to a carbonate group,
Both ends are hydroxyl groups,
A polycarbonate diol composition comprising a polycarbonate diol,
The whole composition contains 5 to 50% by mass of the polyoxyethylene structure represented by (Formula 1), 50 to 95% by mass of the polycarbonate structure represented by (Formula 2), and has a number average molecular weight of 300 to 10000, the composition (hereinafter also referred to as “component (A)” or “(A)”);
(B) polyol component other than (A) (hereinafter also referred to as “(B) component” or “(B)”); and
(C) an isocyanate compound (hereinafter also referred to as “(C) component” or “(C)”);
40-100 mass% of said (A) and 0-60 mass% of said (B) are contained with respect to a total of 100 mass% of said (A) and said (B).

(In formula, m represents the number of 9-50.)

(In the formula, R may be the same or different and each represents an optionally substituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 2 to 15 carbon atoms. And n represents a number from 1 to 50.)

The coating composition of this embodiment can provide the coating film excellent in solvent resistance and sunscreen resistance by taking such a structure. Here, the sunscreen resistance means resistance to sunscreen agents.
The coating composition of the present embodiment preferably contains the polycarbonate diol composition (component (A)) in an amount of 50 to 100% by mass in a total of 100% by mass of (A) and (B). It is more preferable to include 100% by mass.

(Polycarbonate diol composition (component (A)))
The polycarbonate diol composition in the present embodiment contains, in a molecular chain, the polyoxyethylene structure represented by (Formula 1) and the polycarbonate structure represented by (Formula 2), and the polyoxyethylene The terminal structure of the structure is a structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, or a structure in which both terminals are bonded to a carbonate group, and both terminals are hydroxyl groups. A polycarbonate diol composition comprising a polycarbonate diol. The polycarbonate diol composition contains 5 to 50% by mass of the polyoxyethylene structure represented by (Formula 1) and 50 to 95% by mass of the polycarbonate structure represented by (Formula 2) in the whole composition. The number average molecular weight is 300 to 10,000.
In the polycarbonate diol composition in the present embodiment, the structure of each polycarbonate diol is not particularly limited as long as the ratio of the structure of (Formula 1) to the structure of (Formula 2) is in the above range as a whole composition. A component represented by (formula b) described later may be contained.

  The polycarbonate diol contained in the polycarbonate diol composition in this embodiment has hydroxyl groups at both ends. Control of urethanization reaction rate and condition due to impurities in various raw materials used in the production of polycarbonate diol compositions, terminal structures produced as a by-product during the production of polycarbonate diol compositions, or usage applications of polycarbonate diol compositions For this reason, some of the terminal hydroxyl groups may be converted to alkyl groups or aryl groups that do not react with isocyanate groups. In the present embodiment, in consideration of such a case, the terminal group of the polycarbonate diol includes a case where strictly 100 mol% of both terminals is not a hydroxyl group. From this viewpoint, the proportion of hydroxyl groups in the total amount of terminal groups is preferably 90 mol% or more, and more preferably 95 mol% or more. The both terminal structures of the polycarbonate diol composition can be confirmed based on, for example, the method for measuring the terminal hydroxyl group concentration described in Japanese Patent No. 3874664.

  The polycarbonate diol composition in this embodiment contains 5 to 50% by mass of the polyoxyethylene structure represented by the above (Formula 1) in the whole composition. The content of the polyoxyethylene structure is 5% by mass or more because a coating film excellent in solvent resistance and sunscreen resistance tends to be obtained. Moreover, since the content rate of a polyoxyethylene structure tends to suppress decomposition | disassembly by the heat | fever of a polycarbonate diol composition, it is 50 mass% or less. The content of the polyoxyethylene structure is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass.

  M in the above (Formula 1) represents the number of repeating units having an oxyethylene structure, is 9 to 50, preferably 9 to 40, and more preferably 9 to 30. Said m can be calculated | required by carrying out alkali decomposition of a polycarbonate diol composition, taking out a raw material diol component, and performing GC-MS measurement, LC-MS measurement, and a gel permeation chromatography (GPC) measurement about the said component. When m is 9 or more, the amount of polyoxyethylene glycol used as a raw material can be reduced, so that the water resistance and heat resistance of the polycarbonate diol composition of this embodiment tend to be further improved. When m is 50 or less, the crystallinity of the polycarbonate diol composition tends to be suppressed. The (formula 1) is preferably a polyoxyethylene structure represented by (formula 3).

(In the formula, l represents a number of 9 to 30.)

The terminal structure of the polyoxyethylene structure represented by (Formula 1) is a structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, or both terminals are bonded to a carbonate structure. This is the structure.
In the polycarbonate diol composition in this embodiment, the terminal structure of the polyoxyethylene structure has one terminal bonded to a carbonate group and the other terminal bonded to a hydroxyl group, and both terminals bonded to a carbonate structure. It may be mixed with the structure.

  The polycarbonate diol composition in the present embodiment contains 50 to 95% by mass of the polycarbonate structure represented by (Formula 2) in the whole composition. The content of the polycarbonate structure is 50% by mass or more from the viewpoint of the water resistance, heat resistance, chemical resistance, wear resistance and the like of the polycarbonate diol composition. The content of the polycarbonate structure is 95% by mass or less from the viewpoint of the compatibility of the polycarbonate diol composition with the polyether polyol. The content of the polycarbonate structure is preferably 60 to 95% by mass, and more preferably 70 to 95% by mass.

  R in the above (Formula 2) may be the same or different and has 2 to 15 carbon atoms, which may have a branched aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic carbon Represents a hydrogen group. Carbon number of R becomes like this. Preferably it is 3-12, More preferably, it is 3-9. The aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are preferably divalent.

  As said aliphatic hydrocarbon group, a linear or branched alkylene group is mentioned, for example. Specific examples of the linear or branched alkylene group include, for example, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group, hexylene group, isohexylene group, A heptylene group, an isoheptylene group, an octylene group, an isooctylene group, etc. are mentioned. Among these, from the viewpoint of versatility, a butylene group, a pentylene group, an isopentylene group, a hexylene group, and an isohexylene group are preferable.

  When R is an alicyclic hydrocarbon group, the carbon number of R is preferably 6-15, more preferably 6-8. Specific examples of the alicyclic hydrocarbon group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group. Among these, a cyclohexylene group is preferable from the viewpoint of versatility.

  As said aromatic hydrocarbon group, a phenylene group, a naphthylene group, etc. are preferable, for example.

  N in said (Formula 2) represents the number of repeating units of a carbonate structure, and is 1-50, Preferably it is 2-50, More preferably, it is 3-30, More preferably, it is 4-20. . n can be calculated | required by carrying out alkali decomposition of a polycarbonate diol composition, taking out a raw material diol component, and performing GC-MS measurement, LC-MS measurement, and a gel permeation chromatography (GPC) measurement about the said component.

In the present embodiment, the content of the polyoxyethylene structure and the content of the polycarbonate structure in the molecular chain of the polycarbonate diol composition can be determined by ¹ H-NMR measurement. Usually, the hydrogen atom signal of the methylene group of the polyoxyethylene structure is strongly expressed around 3.5 ppm.

  The number average molecular weight of the polycarbonate diol composition in the present embodiment is preferably 300 or more and 10,000 or less, more preferably 400 or more and 10,000 or less, and further preferably 500 or more and 3000 or less. When the number average molecular weight is 300 or more, the flexibility and low temperature characteristics of the thermoplastic urethane obtained from the polycarbonate diol composition tend to be better, and when the number average molecular weight is 10,000 or less, the polycarbonate diol composition There exists a tendency for the moldability of the thermoplastic urethane obtained to become better. The number average molecular weight can be calculated from the hydroxyl value of the polycarbonate diol as in the method described in Examples described later.

  The polycarbonate diol composition in the present embodiment can be obtained by performing a transesterification reaction using a polyoxyethylene diol represented by the following (formula a) and a polycarbonate diol represented by the following (formula b). it can.

(In formula, m represents the number of 9-50.)

(In the formula, R may be the same or different and each represents an optionally substituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 2 to 15 carbon atoms. And n represents a number from 1 to 50.)

  M in the above (formula a) has the same meaning as m in the above (formula 1). R and n in the above (formula b) are respectively synonymous with R and n in the above (formula 2). Hereinafter, the polyoxyethylene diol represented by (Formula a) and the polycarbonate diol represented by (Formula b) will be described.

  The polyoxyethylene diol is not particularly limited as long as it has a structure represented by (formula a). As polyoxyethylenediol, products of various molecular weights are commercially available, and such commercially available products can also be used. Examples of commercially available products of polyoxyethylene diol include “Polyethylene glycol” series manufactured by Wako Pure Chemical Industries, Ltd.

  The number average molecular weight of the polyoxyethylene diol is not particularly limited, but is preferably 400 to 2000, and more preferably 600 to 1500. By using polyoxyethylene glycol having a number average molecular weight of 400 or more, the amount of polyoxyethylene glycol used as a raw material can be reduced, and the water resistance and heat resistance of the polycarbonate diol composition tend to be further improved. . By using polyoxyethylene glycol having a number average molecular weight of 2000 or less, the crystallinity of the polycarbonate diol composition tends to be suppressed.

  The polycarbonate diol is not particularly limited as long as it has a structure represented by (formula b). The method for producing the polycarbonate diol is not particularly limited, and a known method can be employed. For example, a polycarbonate diol can be obtained by reacting a carbonate compound such as alkylene carbonate, dialkyl carbonate, or diaryl carbonate with a diol compound in the presence of a transesterification catalyst.

  Examples of the carbonate compound include, but are not limited to, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate. And alkylene carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate, and diaryl carbonates such as diphenyl carbonate. In this, alkylene carbonate is preferable and ethylene carbonate is more preferable.

  Examples of the diol compound include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Diols having no side chain such as heptanediol, 1,8-octanediol, 1,9-nanodiol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol; 2-methyl-1 , 8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1 Diol having a side chain such as 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol; Cyclic diols such as rhohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis (4-hydroxycyclohexyl) -propane; p-xylenediol, p-tetrachloroxylenediol, 1,4 Examples include diols having an aromatic ring such as bis (hydroxyethoxy) benzene and 2,2-bis [(4-hydroxyethoxy) phenyl] propane. Of these, diols having no side chain are preferred, and 1,5-pentanediol and 1,6-hexanediol are more preferred.

  In the production of the polycarbonate diol represented by the formula (formula b), a transesterification catalyst can be used. The catalyst can be selected from ordinary transesterification catalysts. Specific examples of the transesterification reaction catalyst are not particularly limited, but alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium, calcium, strontium and barium, hydrides, oxydides, amides, carbonic acids. Examples include salts, hydroxides, nitrogen-containing borates, and basic alkali metal salts and alkaline earth metal salts of organic acids. Examples of transesterification catalysts using metals other than alkali metals and alkaline earth metals include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, and niobium. , Molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium metals, salts, alkoxides, and organic compounds. . One or more transesterification catalysts can be selected and used from them. Among these, polycarbonate diols are obtained when one or more transesterification catalysts are used from metals, salts, alkoxides, and organic compounds of sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead, and ytterbium. The transesterification reaction is favorably performed, and the use of the obtained polycarbonate diol is preferable because it has little influence on the urethane reaction. More preferably, magnesium, titanium, ytterbium, tin, or zirconium is used as the transesterification catalyst. Specific examples of the transesterification catalyst include lead acetate trihydrate which is an organic compound of lead, tetraphenyl lead, lead stearate, titanium tetra-n-butoxide which is an organic compound of titanium, and titanium tetra n-propoxy. And titanium tetraisopropoxide are preferred.

  The amount of the transesterification reaction catalyst used is preferably 0.00001% by mass or more and 0.1% by mass or less, and 0.0001% by mass or more and 0.05% by mass with respect to the total amount of raw materials (100% by mass) The following is more preferable.

  The transesterification catalyst used in the transesterification reaction is not consumed in the transesterification reaction when heat treatment is carried out subsequent to the production of the polycarbonate diol, and therefore can be calculated based on the amount of transesterification catalyst used. In the case of using a commercially available polycarbonate diol, the amount of metal in the transesterification catalyst contained in the polycarbonate diol is determined by measuring by ICP (Emission Spectroscopy, Inductively Coupled Plasma).

  For the polycarbonate diol represented by (formula b) used in the production of the polycarbonate diol composition in the present embodiment, a catalyst poison such as a phosphate ester compound is used to deactivate the transesterification reaction catalyst used in the production. It may be added.

  When the raw material polycarbonate diol contains a catalyst poison or the like of the transesterification catalyst used at the time of its production, the polyoxyethylene diol represented by (formula a) in the present embodiment, Since the transesterification reaction with the polycarbonate diol represented by the formula (b) tends to be difficult to proceed, a necessary amount of the above-described transesterification catalyst is newly required in the production of the polycarbonate diol composition (component (A)). Can be added. If the polycarbonate diol represented by (formula b) as a raw material does not contain the catalyst poison of the transesterification reaction catalyst, the transesterification reaction in this embodiment usually tends to proceed. When it is desired to lower the reaction temperature in the production process of the composition (component (A)) or to shorten the reaction time, a necessary amount of a transesterification reaction catalyst can be newly added. In that case, the same transesterification catalyst as used in the production of the polycarbonate diol represented by (formula b) which is the above-mentioned raw material can be employed.

  Further, the polycarbonate diol represented by the raw material (formula b) may be a homopolycarbonate diol obtained from one kind of diol compound or a copolymerized polycarbonate diol obtained from two or more kinds of diol compounds.

  Any of the polycarbonate diols represented by (formula b) as the raw materials exemplified above can obtain the polycarbonate diol composition in the present embodiment by a transesterification reaction with polyoxyethylene diol. A homopolycarbonate diol obtained using 1,6-hexanediol widely used in the market is usually a solid at room temperature, and a polycarbonate diol composition obtained by a transesterification reaction with polyoxyethylenediol is also used. It tends to be solid at room temperature. On the other hand, for example, copolymer polycarbonate diol obtained by using two kinds of 1,5-pentanediol and 1,6-hexanediol is liquid at room temperature and obtained by transesterification with polyoxyethylenediol. The polycarbonate diol composition in this embodiment also tends to be liquid at room temperature. Therefore, from the viewpoint of handleability, the polycarbonate diol as the raw material is often preferred to be liquid at room temperature.

  The number average molecular weight of the polycarbonate diol represented by (formula b) as a raw material is not particularly limited, but is preferably 500 to 5000, and more preferably 1000 to 3000. By using a polycarbonate diol having a number average molecular weight of 500 or more, the performance expected of the polycarbonate diol tends to be further improved. By using a polycarbonate diol having a number average molecular weight of 5000 or less, the increase in viscosity of the polycarbonate diol composition in the present embodiment can be suppressed, and the handling property tends to be further improved.

  The polycarbonate diol composition in the present embodiment can also be produced by using polyoxyethylene diol as a diol and a polycondensation reaction between the polyoxyethylene diol and a carbonate compound. However, in order to proceed such a polycondensation reaction of polycarbonate diol, it is usually necessary to heat at a high temperature for a long time. For this reason, there is a possibility that an undesirable side reaction may occur, and the workload for switching the production type may increase. Also from this viewpoint, it is preferable not to use a polycondensation reaction using polyoxyethylene diol and a carbonate compound as a method for producing the polycarbonate diol in the present embodiment. Also from such a viewpoint, the polycarbonate diol composition in the present embodiment is preferably produced by a transesterification reaction using the polyoxyethylene diol represented by (formula a).

  Specifically, the transesterification reaction can be carried out by mixing the polyoxyethylene diol represented by (formula a) and the polycarbonate diol represented by (formula b) and stirring them while heating. Although the temperature of transesterification is not specifically limited, Preferably it is 120-200 degreeC, More preferably, it is 140-180 degreeC. By making reaction temperature 120 degreeC or more, transesterification can be performed in a shorter time and it is excellent in economical efficiency. By setting the reaction temperature to 200 ° C. or lower, coloring of the obtained polycarbonate diol composition can be prevented.

  The reaction pressure for the transesterification reaction is not particularly limited, but is preferably normal pressure to 1 MPa. Setting the reaction pressure within the above range is preferable from the viewpoint that the reaction can be carried out easily, and in the case of using a secondary material, the transesterification reaction can be performed more efficiently by applying some pressure in consideration of these vapor pressures and the like. It is also preferable from the viewpoint that it can be promoted.

  As a method for controlling the number average molecular weight of the polycarbonate diol composition of the present embodiment, for example, from the viewpoint of selecting an appropriate molecular weight of the polycarbonate diol represented by the formula (formula b), or adjusting the molecular weight, It is preferable to perform a transesterification reaction in the presence of one or more of the above-described alkylene diols.

  The progress and completion of the transesterification reaction can be confirmed by GPC measurement. With the progress of the transesterification reaction, the peak derived from the polyoxyethylene diol represented by the raw material (formula a) gradually decreases with time, and the peak disappears. It is confirmed that a structure derived from polyoxyethylene diol is bonded to the end of the polycarbonate diol represented by

  In the production method of the present embodiment, a step of performing a dehydration treatment of a raw material to be used may be performed as a pretreatment before the above transesterification reaction. In the production method of the present embodiment, after the above-described transesterification reaction, a step of adding the above-described catalyst poison to the transesterification reaction catalyst may be performed as a post-treatment.

(Polyol component other than polycarbonate diol composition (component (B)))
The coating composition of this embodiment contains 0-60 mass% of polyol components (component (B)) other than the polycarbonate diol composition component. The ratio is preferably 0 to 50% by mass.
The polyol component is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule, and examples thereof include polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, and fluorine polyol.

  Although it does not specifically limit as said polyester polyol, For example, polyester polyol, polycaprolactone, etc. are mentioned. The polyester polyol is not particularly limited, and can be obtained, for example, by a condensation reaction between a dibasic acid alone or a mixture and a polyhydric alcohol alone or a mixture. The dibasic acid is not particularly limited. For example, a dibasic acid selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, etc. Examples include acids. The polyhydric alcohol is not particularly limited, and specific examples include polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and the like. Polycaprolactones are not particularly limited, and can be obtained, for example, by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol.

  The acrylic polyol is not particularly limited. For example, an ethylenically unsaturated bond-containing monomer having a hydroxyl group alone or a mixture thereof and another ethylenically unsaturated bond-containing monomer copolymerizable therewith can be used. Those obtained by copolymerization alone or with a mixture may be mentioned.

  The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited. For example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid, Examples include hydroxybutyl acid. Of these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred.

  The other ethylenically unsaturated bond-containing monomer copolymerizable with the ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, and acrylic acid. Acrylic acid such as propyl, isopropyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate Esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid -n-hexyl, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic acid esters such as lauryl crylate, benzyl methacrylate, phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid; acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone Unsaturated amides such as acrylamide, diacetone methacrylamide, maleic acid amide, maleimide; vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate; vinyltrimethoxysilane, vinylmethyl And vinyl monomers having hydrolyzable silyl groups such as dimethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane.

  Although it does not specifically limit as said polyether polyol, For example, the use of hydroxides, such as lithium, sodium, potassium, or strong basic catalysts, such as alcoholate and alkylamine, is individual or a mixture of a polyhydric hydroxy compound. Polyether polyols obtained by adding a single or mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like; obtained by reacting alkylene oxide with a polyfunctional compound such as ethylenediamine Examples of polyether polyols include so-called polymer polyols obtained by polymerizing acrylamide or the like using the above polyethers as a medium.

  The polyvalent hydroxy compound is not particularly limited, and examples thereof include diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like; erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, gatrito Sugar alcohol compounds such as lactitol, rhamnitol; monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesource; trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose And the like; disaccharides such as raffinose, gentianose, and meletitose; and tetrasaccharides such as stachyose.

  The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

  Although it does not specifically limit as a fluorine polyol, For example, it is a polyol containing a fluorine in a molecule | numerator, For example, the fluoro olefin and cyclovinyl ether currently disclosed by Unexamined-Japanese-Patent No. 57-34107, Unexamined-Japanese-Patent No. 61-27511 And copolymers such as hydroxyalkyl vinyl ether and monocarboxylic acid vinyl ester.

(Isocyanate compound (component (C)))
The coating composition of the present embodiment contains an isocyanate compound (component (C)). The isocyanate compound is not particularly limited as long as it functions as a curing agent for the coating composition, and one having two or more isocyanate groups at the terminal is used. Examples of such isocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate. And aromatic diisocyanates such as naphthylene diisocyanate, triphenylmethane-4,4′-4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoene and 4 , 4′-dimethyldiphenylmethane-2,2 ′, 5,5′-tetraisocyanate and other isocyanate compounds having three or more isocyanate groups, as well as Examples include isocyanurate-modified products and biuret-modified products. As a commercial item of an isocyanate compound, Asahi Kasei Corporation 24A-100, 22A-75P, TPA-100, TKA-100, P301-75E, D101, D201, 21S-75E, MFA-75B, MHG-80B, for example , TUL-100, TLA-100, TSA-100, TSS-100, TSE-100, E402-80B, E405-80B, AE700-100, A201H, 17B-60P, TPA-B80E, MF-B60B, MF-K60B , SBB-70P, SBN-70D, E402-B80B, WB40-100, WT30-100, WT31-100, WB40-80D, WT20-100, WL70-100, WE50-100, WM44-L70G ) ”Series, etc. It is.

(Other ingredients)
In addition to the component (A), the component (B), and the component (C), the coating composition of the present embodiment further includes a solvent, a catalyst, urethane beads, a matting agent, a leveling agent, and an anti-settling agent. Other components such as an agent may be included. By appropriately adding these other components, coating compositions having different properties such as a soft feel coating and a clear coating can be obtained.

  As a manufacturing method of the coating composition of this embodiment, the said (A) component is 40-100 mass% with respect to the total of 100 mass% of said (A) component and said (B) component, and said (B) component is added. If it is the method of mixing the said (A) component, the said (B) component, the said (C) component, and the said other component as needed, it will not restrict | limit so that it may contain 0-60 mass%. Specifically, as a method for producing the coating composition of the present embodiment, for example, using a stirrer or the like, after stirring for 5 to 60 minutes at a rotation of 50 to 1000 rpm, a defoaming operation using a vacuum deaerator The method of performing is mentioned.

  The paint composition of the present embodiment includes automobiles, buses, railway vehicles, construction machinery, agricultural machinery, floors and walls and roofs of buildings, metal products, mortar and concrete products, woodwork products, plastic products, calcium silicate plates and plaster. It can be used as a paint for ceramic building materials such as boards.

  Hereinafter, the present embodiment will be described more specifically with specific examples and comparative examples. However, the present embodiment is not limited to these examples and comparative examples unless they exceed the gist thereof. Absent. Evaluation and physical properties in Examples and Comparative Examples described later were evaluated and measured by the following methods. In the examples, unless otherwise specified, “part” and “%” are based on mass.

(Measurement of number average molecular weight)
The number average molecular weight was determined from the hydroxyl value as described later.

(Measurement of hydroxyl value)
The hydroxyl value was measured by the following method.
Using a measuring flask, pyridine was added to 12.5 g of acetic anhydride to 50 ml to prepare an acetylating reagent. The sample was accurately weighed in an amount of 2.5 to 5.0 g in a 100 ml eggplant flask. After adding 5 ml of acetylating reagent and 10 ml of toluene with a whole pipette, a condenser tube was attached, and the mixture was stirred and heated at 100 ° C. for 1 hour. Distilled water (2.5 ml) was added with a whole pipette, and the mixture was further heated and stirred for 10 minutes. After cooling for 2 to 3 minutes, 12.5 ml of ethanol was added, and 2 to 3 drops of phenolphthalein was added as an indicator, and titrated with 0.5 mol / l ethanolic potassium hydroxide. An acetylating reagent (5 ml), toluene (10 ml), and distilled water (2.5 ml) were placed in a 100 ml eggplant flask, heated and stirred for 10 minutes, and then titrated in the same manner (blank test). Based on this result, the hydroxyl value was calculated by the following formula (1).

Hydroxyl value (mg-KOH / g) = {(DC) × 28.05 × f} / E (1)

C represents the sample titer (ml), D represents the blank titer (ml), E represents the sample weight (g), and f represents the titrant factor.
The number average molecular weight of the polycarbonate diol was calculated using the following formula (2).

Number average molecular weight = 2 / (G × 10 ⁻³ /56.11) (2)

  G represents a hydroxyl value (mg-KOH / g).

Evaluation of solvent resistance and sunscreen resistance, which are physical properties of the coating film, was performed as follows.
(Solvent resistance)
On a glass plate (JIS R3202, 75 mm × 150 mm square, 1 mm thickness), a releasable paper adhesive tape was attached as a spacer to both ends of the plate so that the dry film thickness was 40 to 50 μm. The prepared coating composition was dropped onto the top of the plate and coated using (glass rod, diameter 8 mm). After baking at 60 ° C. for 30 minutes, it was dried for 1 week on a horizontal table in an atmosphere of 23 ° C. and 50% RH. A cotton ball impregnated with a solvent (xylene, methyl ethyl ketone, ethanol, oleic acid) is allowed to stand on the surface of the coating for 1 minute in an atmosphere of 23 ° C. and 50% RH on a horizontal table, and scratches and whitening are visually observed. It was evaluated whether any abnormalities such as the above occurred.
In Tables 1 and 2, “◯” represents that there was no change in the coating film appearance, “Δ” represents that there was a slight change in the coating film appearance, and “×” represents the coating film appearance. This indicates that there was a change in swelling, traces, and cloudiness.

(Sun resistance)
On a glass plate (JIS R3202, 75 mm × 150 mm square, 1 mm thickness), the prepared coating composition is dropped on the top of the plate so that the dry film thickness is 40 to 50 μm, and (glass rod, diameter 8 mm) Used and coated. After baking at 60 ° C. for 30 minutes, it was dried for 1 week on a horizontal table in an atmosphere of 23 ° C. and 50% RH. A sunscreen cream (Neutrogena Ultra Sheer DRY-TOUCH SUNSCREEN Broad Spectrum SPF 30) was uniformly applied on the surface of the coating film in an atmosphere of 23 ° C. and 50% RH on a horizontal base and left for 1 hour. Then, using a small amount of neutral detergent, thoroughly wash the surface of the coating film, remove the sunscreen agent, dry on a horizontal table in an atmosphere of 23 ° C. and 50% RH, and then visually. It was evaluated whether abnormalities such as traces of sunscreen and swelling and peeling of the coating film occurred.
In Tables 1 and 2, “◯” represents that there was no change in the coating film appearance, “Δ” represents that there was a slight change in the coating film appearance, and “×” represents the coating film appearance. This indicates that there was a change in swelling, traces, and cloudiness.

(A) Preparation of polycarbonate diol composition [Synthesis Example 1]
After charging 458 g of 1,5-pentanediol, 500 g of 1,6-hexanediol and 760 g of ethylene carbonate, 0.0860 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in a 190 ° C. oil bath and reacted at a reaction temperature of 165 ° C. for 12 hours while part of the distillate was extracted. Thereafter, the reactor was directly connected to a condenser, and the temperature of the oil bath was raised to 180 ° C., and the reaction was further carried out for 2 hours while gradually reducing the pressure. As a result, 855 g of polycarbonate diol that was liquid at room temperature was obtained. . 90 parts by mass of the obtained polycarbonate diol and “polyethylene glycol 1000 (trade name)” (polyoxyethylene diol having a number average molecular weight of about 1000) manufactured by Wako Pure Chemical Industries, Ltd. were charged at a rate of 10 parts by mass, The mixture was heated with stirring and maintained at about 145 ° C. for 6 hours as the temperature inside the reactor. Thereafter, 85% phosphoric acid was added in an amount of 2.0 equivalents with respect to titanium tetra-n-butoxide, and a heat treatment was performed at 115 ° C. for 3 hours as a reactor internal temperature to obtain a polycarbonate diol composition. The hydroxyl value was measured and found to be 108.7. When the number average molecular weight was measured, it was 1032 g / mol. In addition, about transesterification reaction, GPC measurement is performed with respect to the reaction solution over time, and by confirming the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product over time, the progress of the reaction, etc. confirmed. The final obtained polycarbonate diol composition is almost quantitatively based on the amount of raw material charged, and has a corresponding structure. Confirmed by.

[Synthesis Example 2]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was placed in a nitrogen atmosphere, and “Duranol T6002 (trade name)” (as a diol, 1,6- 80 parts by mass of homopolycarbonate diol having a number average molecular weight of about 2000 using hexanediol, manufactured by Wako Pure Chemical Industries, Ltd., “polyethylene glycol 1000 (trade name)” (polyoxy having a number average molecular weight of about 1000) 20 parts by mass of ethylenediol) and titanium tetra-n-butoxide as a transesterification catalyst were charged at a ratio of 200 ppm with respect to the polycarbonate diol as a raw material. These were heated with stirring and maintained at about 150 ° C. for 6 hours as the reactor internal temperature. Then, it cooled to room temperature and obtained the polycarbonate diol composition. When the hydroxyl value was measured, it was 63.5. It was 1767 g / mol when the number average molecular weight was measured. As for the transesterification reaction, the GPC measurement is performed over time for the reaction solution, and the progress of the reaction is confirmed by confirming the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product over time. It was confirmed. The final obtained polycarbonate diol composition is almost quantitatively based on the amount of raw material charged, and has a corresponding structure. Confirmed by.

<Preparation of soft feel paint>
[Comparative Example 1]
Curing 12 g of “Setaqua 6510 (trade name)” (water-based acrylic polyol; hydroxyl value 138.0 mg KOH / g resin, solid content 42 mass%) manufactured by Nuplex as the main agent so that the molar ratio of NCO / OH is 1.25 “WT31-100 (trade name)” (aqueous polyisocyanate; NCO content 17.4%) manufactured by Asahi Kasei Co., Ltd. is used as an agent, 11.25 g of ion-exchanged water as a solvent, and OMG Borchers is used as an aqueous catalyst. 0.16 g of “Borchers LH10 (trade name)”, 3.15 g of “Art Pearl C-800BK (trade name)” manufactured by Negami Kogyo Co., Ltd. as urethane beads, “ACEMATT TS 100 (product of Evonik) as matting agent Name) 1.07 g, “BYK-33” manufactured by BYK as a leveling agent 0.09 g of “1” and 0.09 g of “Disparon AQ-002” manufactured by Enomoto Kasei Co., Ltd. as an anti-settling agent, were each weighed and mixed, stirred for 20 minutes at 600 rpm using a stirrer, and then a vacuum defoamer A defoaming operation was carried out using to obtain a paint. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 2]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 9/1, and the NCO / OH molar ratio is 1.25. Thus, 12 g of “Setaqua 6510 (trade name)” as the main agent and 0.56 g of the polycarbonate composition obtained in Synthesis Example 1, 4.07 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent 12.87 g of exchange water, 0.17 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 3.33 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Trade name) ”is 1.13 g,“ BYK-331 ”is 0.1 g as a leveling agent, Isuparon AQ-002 "and 0.1 g, and mixed taking Ri each amount, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 3]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 8/2, and the NCO / OH molar ratio is 1.25. Thus, 11 g of “Setaqua 6510 (trade name)” as the main agent and 1.16 g of the polycarbonate composition obtained in Synthesis Example 1, 4.11 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent 13.66 g of exchanged water, 0.16 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 3.25 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product Name) ”was 1.11 g,“ BYK-331 ”was 0.1 g as a leveling agent, and“ Isuparon AQ-002 "and 0.1 g, and mixed taking Ri each amount, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 4]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 7/3, and the NCO / OH molar ratio is 1.25. Thus, 10 g of “Setaqua 6510 (trade name)” as the main agent and 1.8 g of the polycarbonate composition obtained in Synthesis Example 1, 4.18 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent 14.59 g of exchange water, 0.16 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 3.2 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product name) ”is 1.09 g,“ BYK-331 ”is 0.1 g as a leveling agent, and Paron AQ-002 "and 0.1 g, and mixed taking Ri each amount, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 1]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 5/5, and the NCO / OH molar ratio is 1.25. Thus, 8 g of “Setaqua 6510 (trade name)” as the main agent, 3.36 g of the polycarbonate composition obtained in Synthesis Example 1, 4.48 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent 17.23 g of exchange water, 0.16 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 3.17 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product Name) ”is 1.08 g,“ BYK-331 ”is 0.1 g as a leveling agent, and“ Suparon AQ-002 "and 0.1 g, and mixed taking Ri each amount, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 2]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 3/7, and the NCO / OH molar ratio is 1.25. Thus, 5 g of “Setaqua 6510 (trade name)” as the main agent, 4.9 g of the polycarbonate composition obtained in Synthesis Example 1, 4.46 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent 18.88 g of exchange water, 0.14 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 2.87 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product name) ”is 0.98 g,“ BYK-331 ”is 0.09 g as a leveling agent, Suparon AQ-002 "and 0.09 g, and mixed taking Ri each amount, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 3]
7 g of the polycarbonate composition obtained in Synthesis Example 1 as the main agent, 4.09 g of “WT31-100 (trade name)” as the curing agent, and ions as the solvent so that the NCO / OH molar ratio is 1.25. 20.19 g of exchange water, 0.11 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 2.22 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product Name) "is 0.75 g," BYK-331 "is 0.07 g as the leveling agent, and" Disparon AQ-002 "is 0.07 g as the anti-settling agent. After stirring at 600 rpm for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 4]
8 g of the polycarbonate composition obtained in Synthesis Example 2 as the main agent, 2.73 g of “WT31-100 (trade name)” as the curing agent, and ions as the solvent so that the NCO / OH molar ratio is 1.25. 19.53 g of exchanged water, 0.11 g of “Borchers LH10 (trade name)” as an aqueous catalyst, 2.15 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product name) 0.73 g, “BYK-331” 0.06 g as a leveling agent, and 0.06 g “Disparon AQ-002” as an anti-settling agent, respectively, were mixed and weighed using a stirrer. After stirring at 600 rpm for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 5]
10 g of “T5652 (trade name)” (polycarbonate diol; hydroxyl value 55.9 mg KOH / g resin, solid content 100 mass%) manufactured by Asahi Kasei Co., Ltd. as the main agent so that the molar ratio of NCO / OH is 1.1. 2 g of “TPA-100 (trade name)” (polyisocyanate; NCO content 23%) manufactured by Asahi Kasei Co., Ltd. as a curing agent, and a mixed solvent of butyl acetate / xylene (butyl acetate / xylene = 50/50 mass%) as a solvent. 21.73 g, 1.2 g dibutyltin dilaurate (diluted with 1% butyl acetate) as catalyst, 2.4 g “Art Pearl C-800BK (trade name)” as urethane beads, “ACEMATT TS 100 (product) as matting agent Name) 0.82g and leveling agent "BYK-331" 0.07g, each weighed and mixed And, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 6]
As the main agent, 8 g of “T5651 (trade name)” (polycarbonate diol; hydroxyl value 109.9 mg KOH / g resin, solid content 100% by mass) manufactured by Asahi Kasei Co., Ltd. was used so that the NCO / OH molar ratio was 1.1. 3.15 g of “TPA-100 (trade name)” (polyisocyanate; NCO content 23%) manufactured by Asahi Kasei Co., Ltd. as a curing agent, and butyl acetate / xylene mixed solvent (butyl acetate / xylene = 50/50 mass%) as a solvent ), 1.11 g of dibutyltin dilaurate (diluted with 1% butyl acetate) as a catalyst, 2.23 g of “Art Pearl C-800BK (trade name)” as urethane beads, and “ACEMATT TS 100 as a matting agent” (Product Name) "is 0.76g, and" BYK-331 "is 0.07g as a leveling agent. Taken mixed, after stirring at 600 rpm 20 minutes using a stirrer to give a paint under defoaming operation with a vacuum defoamer. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 5]
8 g of the polycarbonate composition obtained in Synthesis Example 1 as the main agent so that the NCO / OH molar ratio is 1.1, and “TPA-100 (trade name)” (polyisocyanate; manufactured by Asahi Kasei Corporation) as the curing agent. 3.11 g of NCO content 23%), 20.13 g of butyl acetate / xylene mixed solvent (butyl acetate / xylene = 50/50 mass%) as a solvent, 1 dibutyltin dilaurate (diluted 1% butyl acetate) as a catalyst .11 g, 2.22 g of “Art Pearl C-800BK (product name)” as urethane beads, 0.76 g of “ACEMATT TS 100 (product name)” as matting agent, and “BYK-331” as leveling agent 0 0.07 g, each weighed out and mixed, stirred for 20 minutes at 600 rpm using a stirrer, then defoamed using a vacuum defoamer I went to thereby obtain a coating. Table 1 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

<Preparation of clear paint>
[Comparative Example 7]
In order for the NCO / OH molar ratio to be 1.25, 22 g of “Setaqua 6510 (trade name)” as the main agent, 6.86 g of “WT31-100 (trade name)” as the curing agent, and ion-exchanged water as the solvent 8.76 g, 0.29 g of “Borchers LH10 (trade name)” as an aqueous catalyst, and 0.17 g of “BYK-331” as a leveling agent were weighed and mixed, and stirred at 600 rpm for 20 minutes using a stirrer. Thereafter, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 8]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 9/1, and the NCO / OH molar ratio is 1.25. As described above, 20 g of “Setaqua 6510 (trade name)” as the main agent and 0.98 g of the polycarbonate composition obtained in Synthesis Example 1, 6.78 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent 10.05 g of exchange water, 0.28 g of “Borchers LH10 (trade name)” as an aqueous catalyst, and 0.17 g of “BYK-331” as a leveling agent were weighed and mixed, and the mixture was stirred at 600 rpm using a stirrer. After stirring for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 9]
The resin component mass ratio between “Setaqua 6510 (trade name)” and the polycarbonate diol composition obtained in Synthesis Example 1 is 7/3, and the NCO / OH molar ratio is 1.25. Thus, 16 g of “Setaqua 6510 (trade name)” as the main agent, 2.88 g of the polycarbonate composition obtained in Synthesis Example 1, 6.67 g of “WT31-100 (trade name)” as the curing agent, and ion as the solvent Weighed and mixed 12.8 exchange water, 0.26 g of “Borchers LH10 (trade name)” as an aqueous catalyst, and 0.14 g of “BYK-331” as a leveling agent, and mixed at 600 rpm using a stirrer. After stirring for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 6]
11 g of the polycarbonate composition obtained in Synthesis Example 1 as the main agent, 6.43 g of “WT31-100 (trade name)” as the curing agent, and ions as the solvent so that the NCO / OH molar ratio is 1.25. 24.56 g of exchange water, 0.17 g of “Borchers LH10 (trade name)” as an aqueous catalyst, and 0.1 g of “BYK-331” as a leveling agent were weighed and mixed, and the mixture was stirred at 600 rpm using a stirrer. After stirring for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 7]
12 g of the polycarbonate composition obtained in Synthesis Example 2 as the main agent, 4.1 g of “WT31-100 (trade name)” as the curing agent, and ions as the solvent so that the NCO / OH molar ratio is 1.25. Weighed and mixed 22.68 g of exchange water, 0.16 g of “Borchers LH10 (trade name)” as an aqueous catalyst, and 0.1 g of “BYK-331” as a leveling agent, and mixed at 600 rpm using a stirrer. After stirring for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 10]
A resin component mass ratio of “Setalux 1152 (trade name)” (acrylic polyol; hydroxyl value 138.6 mg KOH / g resin, solid content 61 mass%) manufactured by Nuplex and the polycarbonate diol composition obtained in Synthesis Example 2 is 9 / In order to obtain a mass ratio of 1 and a molar ratio of NCO / OH of 1.1, 20 g of “Setalx 1152 (trade name)” as the main agent and 1. 1 of the polycarbonate composition obtained in Synthesis Example 2 36 g, 6.58 g of “TPA-100 (trade name)” as a curing agent, 9.71 g of butyl acetate as a solvent, 2.79 g of dibutyltin dilaurate (0.1% butyl acetate diluted) as a catalyst, as a leveling agent 0.17 g of “BYK-331” was weighed and mixed, and after stirring for 20 minutes at 600 rpm using a stirrer Under defoaming operation with a vacuum defoamer to obtain a coating material. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 11]
As the main agent, 12 g of “T5652 (trade name)” manufactured by Asahi Kasei Co., Ltd. is used as the main agent, and “TPA-100 (trade name)” manufactured by Asahi Kasei Co., Ltd. is used as the curing agent. 4 g, 20.29 g of butyl acetate as a solvent, 1.44 g of dibutyltin dilaurate (diluted with 0.1% butyl acetate) as a catalyst, 0.09 g of “BYK-331” as a leveling agent, respectively, and mixed, After stirring for 20 minutes at 600 rpm using a stirrer, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Comparative Example 12]
2. As a main agent, 10 g of “T5651 (trade name)” manufactured by Asahi Kasei Co., Ltd., and “TPA-100 (trade name)” manufactured by Asahi Kasei Co., Ltd. as a curing agent so that the NCO / OH molar ratio is 1.1. 94 g, 19.63 g of butyl acetate as a solvent, 1.39 g of dibutyltin dilaurate (diluted with 0.1% butyl acetate) as a catalyst, 0.08 g of “BYK-331” as a leveling agent, respectively, and mixed. After stirring for 20 minutes at 600 rpm using a stirrer, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

[Example 8]
15 g of the polycarbonate composition obtained in Synthesis Example 1 as the main agent, 5.84 g of “TPA-100 (trade name)” as the curing agent, and acetic acid as the solvent so that the NCO / OH molar ratio is 1.1. Weigh and mix 18.88 g of butyl, 2.08 g of dibutyltin dilaurate (0.1% butyl acetate dilution) as a catalyst, and 0.13 g of “BYK-331” as a leveling agent, and use a stirrer. After stirring at 600 rpm for 20 minutes, a defoaming operation was performed using a vacuum defoamer to obtain a paint. Table 2 shows the solvent resistance and sunscreen resistance of the coating film formed from the obtained paint.

  From the above, it was confirmed that the coating film formed from the coating composition of this example was excellent in solvent resistance and sun resistance.

  The coating composition of the present invention includes automobiles, buses, railway vehicles, construction machinery, agricultural machinery, floors and walls and roofs of buildings, metal products, mortar and concrete products, woodwork products, plastic products, calcium silicate boards and gypsum boards It can be suitably used in a wide range of fields such as paints for ceramic building materials.

Claims (3)

(A) The molecular chain contains a polyoxyethylene structure represented by (Formula 1) and a polycarbonate structure represented by (Formula 2),
The terminal structure of the polyoxyethylene structure is a structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, or a structure in which both terminals are bonded to a carbonate group,
Both ends are hydroxyl groups,
A polycarbonate diol composition comprising a polycarbonate diol,
The whole composition contains 5 to 50% by mass of the polyoxyethylene structure represented by (Formula 1), 50 to 95% by mass of the polycarbonate structure represented by (Formula 2), and has a number average molecular weight of 300 to A composition that is 10,000;
(B) a polyol component other than (A) above; and
(C) an isocyanate compound;
The coating composition which contains 40-100 mass% of said (A), and 0-60 mass% of said (B) with respect to a total of 100 mass% of said (A) and said (B).
(In formula, m represents the number of 9-50.)
(In the formula, R may be the same or different and each represents an optionally substituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 2 to 15 carbon atoms. And n represents a number from 1 to 50.)   The polycarbonate diol composition comprises, in the whole composition, 5 to 30% by mass of the polyoxyethylene structure represented by (Formula 1) and 70 to 95% by mass of the polycarbonate structure represented by (Formula 2). The coating composition of Claim 1 containing these. The coating composition of Claim 1 or 2 whose said polyoxyethylene structure is a polyoxyethylene structure represented by (Formula 3).
(In the formula, l represents a number of 9 to 30.)