JP5344852B2 - Curable coating composition containing polycarbonate diol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a curable coating material capable of forming a coating film having not only an excellent balance of physical properties between physical strength of the coating film such as flexibility, abrasion resistance or the like of the coating film and chemical resistance of the coating film such as acid resistance, alkali resistance, alcohol resistance, resistance to oleic acid or the like but also a soft touch feel. <P>SOLUTION: The composition for a curable coating material essentially comprises the components (a), (b) and (c) as follows: the component (a) is a polyisocyanate compound having at least two isocyanate groups in a molecule; the component (b) is an aliphatic polycarbonate diol composed of a repeating unit of formula (1) and a repeating unit of the following formula (2), -[-O-(-CH<SB>2</SB>-)<SB>4</SB>-O-CO-]-; and the component (c) is a silica-based matting agent having an average particle size of 0.1-10 &mu;m. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polyisocyanate compound having at least two isocyanate groups in one molecule, a polycarbonate diol having at least two hydroxyl groups in one molecule represented by a specific structural formula, and a specific The present invention relates to a curable coating composition comprising a matting agent having an average particle diameter of

  Conventionally, polyurethane resins are used in a wide range of areas such as synthetic leather, artificial leather, adhesives, furniture paints, and automobile paints, and polyethers and polyesters have been used as polyol components that react with isocyanates. However, in recent years, the physical resistance of the resin itself, such as heat resistance, weather resistance, and abrasion resistance, and the sophistication of the chemical resistance of the resin such as hydrolysis, weather resistance, oil resistance, etc. There is a growing demand for paints that are practically incompatible with physical strength and that are soft to the touch. In general, in order to improve physical strength such as wear resistance and chemical resistance such as chemical resistance, it is common to introduce a crosslinked structure into the polymer. Since it becomes hard, it has been difficult to achieve both a high level of demand for resistance and a soft hand.

  The present invention is excellent in physical strength such as flexibility and abrasion resistance of the coating film, and excellent in chemical resistance such as acid resistance, alkali resistance, alcohol resistance, and oleic acid resistance. It aims at providing the curable coating composition which enables film formation.

As a result of intensive studies, the present inventors have found that a desired object can be achieved by combining a polyisocyanate curing agent, a polycarbonate diol having a specific structure, and a matting agent having a specific average particle size. Invented.
(1) (a) a polyisocyanate compound having at least two isocyanate groups in one molecule;
(B) It consists of repeating units of the following formulas (1) and (2), and the ratio of (1) and (2) is (1) / (2) = 90/10 to 30/70 (molar ratio). An aliphatic polycarbonate diol having a number average molecular weight of 550 to 3500 and having a hydroxyl group as a terminal group; and

（ｃ）平均粒子径が０．１から１０μｍのシリカ系艶消し剤
を必須成分として含有する硬化性塗料用組成物であって、前記（ｃ）のシリカ系艶消し剤を、前記硬化性塗料用組成物の全固形分において３から３０質量％含有する組成物。
（２） 前記硬化性塗料組成物が、更に下記（ｄ）を前記硬化性塗料用組成物の全固形分において０から３０質量％含有する（但し、０質量％は除く）、（１）に記載の硬化性塗料用組成物；
（ｄ）平均粒子径が２〜２０μｍのポリウレタン粒子。
（３） 前記ポリイソシアナート化合物（ａ）が、１分子中に少なくとも２．５以上のイソシアナート基を有する、（１）又は（２）に記載の硬化性塗料用組成物。
（４） 更に不活性有機溶剤を０から９０質量％含有する（但し、０質量％は除く）、（１）又は（２）記載の硬化性塗料用組成物。

(C) A composition for a curable coating containing, as an essential component, a silica-based matting agent having an average particle size of 0.1 to 10 μm, wherein the silica-based matting agent (c) is used as the curable coating A composition containing 3 to 30% by mass in the total solid content of the composition.
(2) The curable coating composition further contains the following (d) in an amount of 0 to 30% by mass (excluding 0% by mass) in the total solid content of the curable coating composition (1): The composition for a curable coating according to the description;
(D) Polyurethane particles having an average particle size of 2 to 20 μm.
(3) The curable coating composition according to (1) or (2), wherein the polyisocyanate compound (a) has at least 2.5 or more isocyanate groups in one molecule.
(4) The curable coating composition according to (1) or (2), further containing 0 to 90% by mass of an inert organic solvent (excluding 0% by mass).

  According to the present invention, the physical strength of the coating film such as flexibility and abrasion resistance of the coating film and the physical property balance of the chemical resistance of the coating film such as acid resistance, alkali resistance, alcohol resistance, oil resistance, etc. It is possible to provide a curable coating composition that enables formation of a coating film that is excellent and soft to the touch.

  Hereinafter, the present invention will be described in detail. Polyisocyanate compounds having at least two or more isocyanate groups in one molecule used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, diisocyanate cyclohexane, tridendiisocyanate, hexamethylene diisocyanate. Narate, trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 2,6-diisocyanate methylcaproate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4 (or Aromatic, aliphatic, and alicyclic isocyanates such as 2,6) -diisocyanate and 4,4'methylenebis (cyclohexyl isocyanate) can be mentioned. Examples of the polyisocyanate compound include isocyanurate-type polyisocyanates and burette-type isocyanates derived from these isocyanates singly or as a mixture, and these diisocyanates and ethylene glycol, polyether polyols (polyethylene glycol, polypropylene). Glycol, etc.), caprolactone polyol, polycarbonate polyol, random type adducts with low molecular weight polyester resins (including oil-modified types) having functional groups that react with isocyanate groups, acrylic copolymers, 2-hydroxypropyl, etc. A vinyl monomer having an isocyanate group and a copolymerizable unsaturated group such as (meth) acrylate and hexamethylene diisocyanate equimolar adduct, isocyanate ethyl (meth) acrylate, etc. Copolymers thereof having an isocyanate group obtained as Sunari min. In particular, from the viewpoint of weather resistance, polyisocyanates derived from aliphatic alicyclic diisocyanates such as hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are preferred. Furthermore, these polyisocyanates are blocked with known blocking agents such as lower alcohols such as butanol and 2-ethylhexanol, methyl ethyl ketone oximes, lactams, phenols, imidazoles, and active methylene compounds. An isocyanate curing agent can be used. Examples of these polyisocyanate compounds include Sumidur 44S and 44V70 (all manufactured by Sumika Bayer Urethane), Dismodule HL (manufactured by Sumika Bayer Urethane), a copolymer of TDI (tolylene diisocyanate) and HDI, and Asahi Kasei Chemicals Duranate 24A-100, Duranate 22A-75PX, Duranate 18H-70B, Duranate 21S-75E, Duranate THA-100, Duranate TPA-100, Duranate MFA-75X, Duranate TSA-100, Duranate TSS-100, Duranate TSE-100, Duranate D-101, Duranate D-201, Duranate P-301-75E, Duranate E-402-90T, Duranate -402-90T, Duranate E-405-80T, Duranate ME20-100, Duranate 17B-60PX, Duranate TPA-B80X, Duranate MF-B60X, Duranate E-402-B80T, Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100, Duranate WT30-100, Duranate MHG-80B, etc. are available. In order to improve the acid resistance, alkali resistance, alcohol resistance, oil resistance, abrasion resistance and scratch resistance of the cured coating film, the polyisocyanate compound contains at least 2.5 or more isocyanate per molecule. And / or a blocked isocyanate group, specifically, diisocyanate derivatives such as biuret, allophanate, uretidinedione, isocyanurate, and polyhydric alcohol adduct type are more preferable.

  These polyisocyanate compounds can be used in combination of two or more.

  The polycarbonate diol used in the present invention comprises repeating units of the following formulas (1) and (2), and the ratio of (1) and (2) is (1) / (2) = 90 / 10-30 / 70 (moles). The aliphatic polycarbonate diol is characterized in that the terminal group is a hydroxyl group.

本発明者らは、各種ポリカーボネートジオールを本用途に検討した結果、上記特定の構造のカーボネートジオールを用いることにより、磨耗性等の物理的強度と化学的耐性のバランスに優れた塗料が得られることを見出した。

As a result of examining various polycarbonate diols for this application, the present inventors can obtain a paint having a good balance between physical strength such as abrasion and chemical resistance by using the carbonate diol having the above specific structure. I found.

  Although the effect generation mechanism of the present invention is not well understood, the total number of carbonate groups per unit weight is compared with conventionally used polycarbonate diol obtained from 1,5-pentanediol and 1,6-hexanediol. Therefore, it is expected that the wear resistance and chemical resistance are improved due to the strong intermolecular interaction between the polymer chains. In addition, the fact that the flexibility of the resin itself hardly changes even when the interaction between polymers is increased is expected due to the side chain methyl group of 2-methyl-1,3-propanediol.

  The polycarbonate diol of the present invention can be produced by various methods described in Schell, Vol. 9 and pages 9 to 20 (1964) by 2-methyl-1,3-propanediol and 1,4-butane. It is a copolymerized polycarbonate diol synthesized from a diol.

  If the ratio of (1) and (2), which are the repeating units constituting the polycarbonate diol, exceeds (1) / (2) = 90/10 (molar ratio), the flexibility of the resulting coating film is impaired, which is preferable. Absent. Further, even when the ratio of (1) and (2) which are repeating units constituting the polycarbonate diol is less than (1) / (2) = 30/70 (molar ratio), the flexibility of the obtained coating film is only impaired. However, oil resistance and abrasion resistance are also deteriorated, which is not preferable. The ratio of (1) and (2) which are repeating units constituting a more preferable polycarbonate diol is (1) / (2) = 85/15 to 35/65 (molar ratio), more preferably (1) / (2 ) = 80/20 to 40/60 (molar ratio).

  The polycarbonate diol used in the present invention is a copolymerized polycarbonate diol synthesized from 2-methyl-1,3-propanediol and 1,4-butanediol, but other low molecular weight diols as long as the characteristics are not impaired. Can be contained as a copolymerization component. Other diols that can be specifically used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, -Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2,3-butanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecadiol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like, and the ratio of these diols is 2-methyl-1,3-propyl. As a percentage of total monomer diol comprising a propanediol and 1,4-butanediol, less than 40 wt%, preferably less than 20 wt%, more preferably less than 10 wt%.

  In the present invention, the number average molecular weight of the polycarbonate diol is 550 to 3500, and more preferably the number average molecular weight is 700 to 3000. When the number average molecular weight is less than 500, the flexibility of the coating film may be lowered. Also, if the number average molecular weight exceeds 3500, the reaction with the isocyanate is remarkably slow and not only takes a long time for drying, but also the viscosity of the resulting coating composition becomes high, making actual coating difficult. It is not preferable.

  It is preferable that the polymer terminal of the polycarbonate diol used in the present invention is substantially all hydroxyl groups.

  In the present invention, in addition to 2-methyl-1,3-propanediol and 1,4-butanediol, compounds having three or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexane Polyfunctionalized polycarbonates having an average number of hydroxyl groups in one molecule of less than 2.5, preferably less than 2.4, obtained by using a smaller amount of triol, pentaerythritol and the like are also included. In the case of a polycarbonate polyfunctionalized to 2.5 or more, the viscosity of the resulting coating composition is increased, and not only is actual coating difficult, but the resulting coating film may be hard, which is not preferable.

  The amount of polyisocyanate added is determined by the molar ratio of NCO in the polyisocyanate and OH in the polycarbonate diol. The blending ratio of the polycarbonate diol and the polyisocyanate is OH / NCO = 1 / 0.5 to 1 / 1.5 (equivalent ratio), more preferably OH / NCO = 1/0. It mix | blends so that it may become 8-1 / 1.2 (equivalence ratio). If the NCO is less than 0.5 equivalent with respect to 1 equivalent of OH, the predetermined coating film properties cannot be obtained, and if it exceeds 1.5 equivalent, the curing rate is not appropriate and is not preferred.

  In the present invention, a silica-based matting agent is used in order to further improve the strength of the coating film surface, improvement of blocking properties and scratch resistance, and to adjust the gloss of the coating film. Examples of silica matte that can be used include finely divided silica, colloidal silica, etc., Degussa AcemattOK, TS, OP, HK series, Fuji Silysia Chemical Co., Ltd. Cicilia, Silo Hovic, Cyrossphere series, There are Quatron series manufactured by Fuso Chemical Co., Ltd., Fine Seal manufactured by Tokuyama Co., Ltd., Nipsil series manufactured by Tosoh Silica Co., Ltd., and Mizusaka Chemical Co., Ltd.

  The average particle size of the matting agent particles used is 0.1 to 10 μm. If the average particle size is less than 0.1 μm, not only the gloss of the resulting coating film becomes too high, but also the feeling of softness to the touch (hereinafter referred to as soft feeling) decreases, which is not preferable. On the other hand, if the average particle diameter exceeds 10 μm, the wear resistance of the resulting coating film is lowered and the transparency of the coating film is impaired, which is not preferable. A more preferable average particle diameter is 0.2 to 8 μm, and further preferably 0.5 to 5 μm.

  The addition amount of the silica-based matting agent particles in the present coating composition part is 3 to 30% by mass of the total solid content contained in the coating composition. When the content of the silica-based matting agent particles is less than 3% by mass, the resulting coating film cannot have a soft feeling, and when the content of the silica-based matting agent particles exceeds 30% by mass, the resulting coating film is obtained. This is not preferable because the wear resistance of the material is extremely deteriorated. The amount of silica-based matting agent particles added is preferably 5 to 20% by mass, more preferably 8 to 15% by mass.

  In the present invention, resin beads may be used in order to enhance the soft feeling of the obtained coating film. Of these, polyurethane particles are preferred. The polyurethane particles are produced by dispersing a polyurethane prepolymer in water in the presence of a suspension stabilizer, polymerizing, washing and drying (Japanese Patent Laid-Open No. 1-185648), non-existing in the presence of an emulsifier. Spherical polyurethane particles synthesized by a method of emulsion polymerization of polyurethane in a water-inert liquid (Japanese Patent Laid-Open No. 5-214054, Japanese Patent Laid-Open No. 7-97425). In the synthesis of this polyurethane particle, when a difunctional or lower isocyanate urethane prepolymer is used, a thermoplastic urethane particle is obtained, and when a terminal isocyanate urethane prepolymer exceeding 2 functions is used, a three-dimensionally crosslinked urethane particle is obtained. It is done. The polyurethane particles used in the present invention include three-dimensional cross-linking in order to improve the acid resistance, alkali resistance, alcohol resistance, oil resistance, heat resistance, and wear resistance of the coating film obtained by the present coating composition. The urethane particles used are more preferably used. The average particle diameter of the polyurethane particles used is 2 to 20 μm. If the average particle size is less than 2 μm, the resulting coating film has high gloss, and not only does not give a high-class feeling, but also the soft feeling is lowered. On the other hand, if the average particle diameter exceeds 20 μm, the wear properties of the resulting coating film are lowered, and the softness of the surface is impaired, which is not preferable. A more preferable average particle diameter is 4 to 15 μm, and further preferably 5 to 10 μm.

  The addition amount of the polyurethane particles in the present coating composition part is 0 to 30% by mass of the total solid content contained in the coating composition. When the content of the polyurethane particles exceeds 30% by mass, the wear properties of the resulting coating film are deteriorated, which is not preferable. The amount of polyurethane particles added is preferably 3 to 20% by mass, more preferably 5 to 15% by mass.

  The curable coating composition of the present invention includes a curing accelerator (catalyst), a filler, a flame retardant, a dye, an organic or inorganic pigment, a release agent, a fluidity modifier, a plasticizer, and an antioxidant according to various uses. An agent, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a colorant, a solvent and the like can be added.

  Curing accelerators include monoamine triethylamine, N, N-dimethylcyclohexylamine, diamine tetramethylethylenediamine, other triamines, cyclic amines, alcohol amines such as dimethylethanolamine, ether amines, and metal catalysts such as potassium acetate. , Potassium 2-ethylhexanoate, calcium acetate, lead octylate, dibutyltin dilaurate, tin octylate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octylate, zinc neodecanoate, phosphine Commonly used materials such as phospholine can be used.

  As fillers and pigments, woven fabric, glass fiber, carbon fiber, polyamide fiber, mica, kaolin, bentonite, metal powder, azo pigment, carbon black, clay, silica, talc, gypsum, alumina white, barium carbonate, etc. Can be used.

  Moreover, about a matting agent and a resin bead, you may use together one or more types of matting agents and a resin bead as needed.

  As the mold release agent, fluidity adjusting agent, and leveling agent, silicone, aerosil, wax, stearate, polysiloxane such as BYK-331 (manufactured by BYK Chemical Co., Ltd.) and the like are used.

  As the additive used in the present invention, at least an antioxidant, a light stabilizer and a heat stabilizer are preferably used. These antioxidants include phosphoric acid, phosphorous acid, aliphatic, aromatic or alkyl group-substituted aromatic esters and hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diesters. Phosphorous compounds such as phosphites and dialkylbisphenol A diphosphites; phenol derivatives, especially hindered phenol compounds, thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates and other sulfur-containing compounds; Tin compounds such as dibutyltin monoxide can be used. These may be used alone or in combination of two or more.

  The coating composition of the present invention may contain 0 to 90% by mass of an inert organic solvent as necessary in order to improve the workability during coating. The inert organic solvent used is an organic solvent which is substantially inert to the polyisocyanate compound and does not have active hydrogen. Examples include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane and methylcyclohexane, fluorine such as trichlorofluoroethane, tetrachlorodifluoroethane, and perfluoroether. Fluorine-type inert liquids such as chemical oils, perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro-n-butylamine, perfluoropolyether, dimethylpolysiloxane and the like alone or in combination. Furthermore, solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene and the like can be mentioned.

  As a coating method of this composition, after mixing each component just before coating, the method of apply | coating to a base material with a spray, a roll, a brush etc. is used. It is also possible to apply a method in which components other than the component (a), which is a curing agent, are mixed in advance, and the component (a) is added and mixed uniformly immediately before application, and then applied.

  The curable coating composition of the present invention can be preferably used as a soft feel coating for home appliances, OA products, automobile interior parts, leather surface treatment, synthetic leather surface treatment, surface treatment of woodworking products such as furniture, and the like. .

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example etc., this invention is not limited at all by these examples. In the following examples and comparative examples, various polyols and various physical properties of the polyurethane film were tested according to the following test methods.

<Test method>
1. OH value 12.5 g of acetic anhydride was diluted with 50 ml of pyridine to prepare an acetylating reagent. A sample to be measured is accurately weighed in an amount of 2.5 to 5.0 g in a 100 ml eggplant flask. Add 5 ml of acetylating reagent and 10 ml of toluene with a whole pipette, attach a condenser, and stir and heat at 100 ° C. for 1 hr. Add 2.5 ml of distilled water with a whole pipette and stir for 10 min. After cooling for 2 to 3 minutes, 12.5 ml of ethanol is added, and after adding 2-3 drops of phenolphthalein as an indicator, titration is performed with 0.5 mol / l ethanolic potassium hydroxide. 5 ml of an acetylating reagent, 10 ml of toluene, and 2.5 ml of distilled water are placed in a 100 ml eggplant flask and stirred for 10 minutes, and then titrated in the same manner (blank test). Based on this result, the OH value was calculated by the following formula (i).
OH value (mg-KOH / g) = {(ba) × 28.05 × f} / e (i)
a: Titration volume of sample (ml)
b: Titrate of blank test (ml)
e: Sample weight (g)
f: Factor of titrant

2. Molecular weight The terminals of the polymers in Examples and Comparative Examples were substantially all hydroxyl groups as determined by ¹³ C-NMR (270 MHz). Furthermore, when the acid value in the polymer was measured by titration with KOH, all of the polymers of Examples and Comparative Examples were 0.01 or less. Therefore, the number average molecular weight of the obtained polymer is obtained by the following formula (ii).
Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.11) (ii)

3. Copolymerization composition ratio The copolymerization composition ratio of the polycarbonate diol of the present invention was measured as follows.
Take 1 g of a sample in a 100 ml eggplant flask, add 30 g of ethanol and 4 g of potassium hydroxide, and react at 100 ° C. for 1 hr. After cooling to room temperature, add 2-3 drops of phenolphthalein to the indicator and neutralize with hydrochloric acid. After cooling in the refrigerator for 1 hr, the precipitated salt was removed by filtration and analyzed by gas chromatography. The analysis was performed by using gas chromatography GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J & W) as a column, diethylene glycol diethyl ester as an internal standard, and a detector as FID. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.

4). Coating film hardness The film formed on the glass plate was measured with a pen drum hardness meter. The coating sample applied on the glass plate was placed in the apparatus, and the time from when the amplitude reached 5 ° until the amplitude reached 2 ° was measured (t). The same measurement was performed on the uncoated glass plate, and the time from when the amplitude reached 5 ° to when the amplitude reached 2 ° was measured (t ₀ ). The hardness (X) was calculated by the following formula. The larger the value, the harder the coating surface.
Hardness: X = t / t ₀

5. Abrasion resistance It measured using the Taber type abrasion tester according to the method of JIS K5600-5-8. The weight before the abrasion test and the change in the weight of the coated film after the abrasion test (500 rotations) were measured and expressed.

6). Glossiness The glossiness of the coating film surface at 85 ° was measured according to the method of JIS K5600-4-7.

7). Soft feeling The soft feeling was evaluated by touching the surface of the coating film with a hand. Judgment results were expressed in the following notation.
◎: Very good soft feeling ○: Good soft feeling △: Good soft feeling ×: It is not felt soft

8). Stickiness Feeling was evaluated by touch when the surface of the coating film was touched by hand. Judgment results were expressed in the following notation.
○: Not sticky △: Slightly sticky ×: Sticky

9. Liquid resistance 1) Acid resistance: The appearance of the coating film after visual immersion in a 0.1N H ₂ SO ₄ aqueous solution at room temperature for 24 hours is visually determined.
◎: No change in appearance ○: Almost no change in appearance △: Very small bulge
X: Clear bulge 2) Alkali resistance: Visual determination of the appearance of the coating film after immersion in a 0.1N NaOH aqueous solution at room temperature for 24 hours.
◎: No change in appearance ○: Almost no change in appearance △: Very small bulge
X: Clear blistering 3) Ethanol resistance: The appearance of the coating film after visual immersion in a 50% aqueous EtOH solution at room temperature for 4 hours is visually judged.
◎: No change in appearance ○: Almost no change in appearance △: Very small bulge
X: Clear swelling 4) Oleic acid resistance: 0.1 g of oleic acid was adhered on the coating film, and the appearance of the coating film was visually determined after 4 hours.
◎: No change in appearance ○: Almost no change in appearance △: Very small bulge
×: Clear blister

Production Example 1
A 2 L separable flask equipped with a stirrer, thermometer, Oldershaw with vacuum jacket having a reflux head at the top was charged with 528 g of 2-methyl-1,3-propanediol, 132 g of 1,4-butanediol, and 650 g of ethylene carbonate. After stirring and dissolving at 70 ° C., 0.015 g of lead acetate trihydrate was added as a catalyst. The mixture was heated in an oil bath set at 175 ° C., and the reaction was carried out for 12 hours while part of the fraction was removed from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 140 ° C. and a vacuum of 1.0 to 1.5 kPa. Thereafter, the Oldershaw was replaced with a simple distillation apparatus, heated in an oil bath set at a temperature of 180 ° C., the flask was cooled to an internal temperature of 140 to 150 ° C. and the vacuum level was reduced to 0.5 kPa, and remained in the separable flask. Diol and ethylene carbonate were removed. Thereafter, the set temperature of the oil bath was raised to 185 ° C., and the reaction was further performed for 4 hours while removing the diol produced at an internal temperature of the flask of 160 to 165 ° C. By this reaction, a viscous liquid was obtained at room temperature. The obtained reaction product had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 80/20 (molar ratio).

Production Example 2
Synthesis was performed in the same manner as in Production Example 1 except that 330 g of 2-methyl-1,3-propanediol and 330 g of 1,4-butanediol were used. The obtained reaction product had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (molar ratio).

Production Example 3
Synthesis was performed in the same manner as in Production Example 1 except that 231 g of 2-methyl-1,3-propanediol and 429 g of 1,4-butanediol were used. The obtained reaction product had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 35/65 (molar ratio).

Production Example 4
In a 2 L separable flask of Production Example 1, 330 g of 2-methyl-1,3-propanediol, 330 g of 1,4-butanediol and 650 g of ethylene carbonate were charged and stirred and dissolved at 70 ° C., followed by lead acetate trihydrate as a catalyst. 0.015 g of Japanese product was added. The mixture was heated in an oil bath set at 175 ° C., and the reaction was carried out for 12 hours while part of the fraction was removed from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 140 ° C. and a vacuum of 1.0 to 1.5 kPa. Thereafter, the Oldershaw was replaced with a simple distillation apparatus, heated in an oil bath set at a temperature of 180 ° C., the flask was cooled to an internal temperature of 140 to 150 ° C. and the vacuum level was reduced to 0.5 kPa, and remained in the separable flask. Diol and ethylene carbonate were removed. The obtained reaction product had an OH value of 140.3 (molecular weight 800) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (molar ratio).

Production Example 5
Synthesis was performed in the same manner as in Production Example 1 except that 627 g of 2-methyl-1,3-propanediol and 33 g of 1,4-butanediol were used. The obtained reaction product had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 95/5 (molar ratio).

Production Example 6
Synthesis was performed in the same manner as in Production Example 1 except that 132 g of 2-methyl-1,3-propanediol and 528 g of 1,4-butanediol were used. The obtained reaction product had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 20/80 (molar ratio).

Production Example 7
Synthesis was performed in the same manner as in Production Example 4 except that 330 g of 2-methyl-1,3-propanediol and 330 g of 1,4-butanediol were used. The obtained reaction product had an OH value of 224.4 (molecular weight of 500) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (molar ratio).

Production Example 8
In Production Example 1, when 330 g of 2-methyl-1,3-propanediol and 330 g of 1,4-butanediol were used, and when the setting of the oil bath was raised to 185 ° C., the internal temperature of the flask was 160 to 165. The synthesis was performed in the same manner except that the time for removing the produced diol was extended at 0 ° C. The obtained reaction product had an OH value of 28.1 (molecular weight 4000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (molar ratio).

Production Example 9
Synthesis was performed in the same manner as in Production Example 1, except that 382 g of 1,5-pentanediol and 433 g of 1,6-hexanediol were used. The obtained reaction product had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio).

Example 1
Polycarbonate diol obtained in Production Example 1 (PCDL-1: polycarbonate diol obtained by copolymerizing 2-methyl-1,3-propanediol and 1,4-butanediol at a molar ratio of 80/20) , Molecular weight 2000) 41.58 g, matting agent Acematt OK-500 (average particle size 3 μm, manufactured by Degussa) 5 g, leveling agent BYK-331 (manufactured by BYK Chemical) 0.75 g, dibutyltin dilaurate (manufactured by Air Products) A mixed solvent of 1.25 g and xylene / butyl acetate (70/30) as a thinner was added so that the final coating solid content would be 50%, and stirred to obtain a coating material. 8.42 g of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals Co., Ltd .: hexamethylene diisocyanate-based isocyanurate type curing agent, solid content 100%, NCO content = 23.1 wt%) as a curing agent was added and mixed and coated. A liquid was prepared. This was coated on an acrylonitrile-butadiene-styrene (ABS) resin plate and then cured by heating at 80 ° C. for 2 hours to obtain a coating film having a film thickness of 30 to 40 μm. Table 1 shows the coating composition and various physical properties.

Example 2
Instead of the polycarbonate diol of Example 1, the polycarbonate diol-2 prepared in Production Example 2 (PCDL-2: 2-methyl-1,3-propanediol and 1,4-butanediol at a molar ratio of 50/50. A paint was prepared in the same manner as in Example 1 except that the polycarbonate diol obtained by copolymerization used a number average molecular weight of 2000). Table 1 shows the coating composition and various physical properties.

Example 3
Instead of the polycarbonate diol of Example 1, the polycarbonate diol-3 prepared in Production Example 3 (PCDL-3: 2-methyl-1,3-propanediol and 1,4-butanediol in a molar ratio of 35/65 A paint was prepared in the same manner as in Example 1 except that the polycarbonate diol obtained by copolymerization used a number average molecular weight of 2000). Table 1 shows the coating composition and various physical properties.

Example 4
Instead of the polycarbonate diol of Example 1, polycarbonate diol-4 prepared in Production Example 4 (PCDL-4: 2-methyl-1,3-propanediol and 1,4-butanediol in a molar ratio of 50/50 A paint was prepared in the same manner as in Example 1 except that the polycarbonate diol obtained by copolymerization used 33.2 g of number average molecular weight 800) and the addition amount of Duranate TPA-100 was 16.8 g. . Table 1 shows the coating composition and various physical properties.

Example 5
Instead of the curing agent of Example 2, Duranate 24A-100 (Asahi Kasei Chemicals Corporation: hexamethylene diisocyanate burette type curing agent, solid content 100%, NCO content = 23.5 wt%) was 8.29 g. A paint was prepared in the same manner as in Example 2 except for the above. Table 1 shows the coating composition and various physical properties.

Example 6
A coating material was produced in the same manner as in Example 2 except that the amount of the matting agent OK-500 added in Example 2 was changed to 15 g. The coating composition and various physical properties are shown in Table 1.

Example 7
A coating material was prepared in the same manner as in Example 2 except that the amount of the matting agent OK-500 added in Example 2 was 3 g. The coating composition and various physical properties are shown in Table 1.

Example 8
A coating material was prepared in the same manner as in Example 2 except that 5 g of silica 1 (particle size 0.5 μm) was used instead of the matting agent OK-500 in Example 2. The coating composition and various physical properties are shown in Table 1.

Example 9
A coating material was prepared in the same manner as in Example 2 except that 5 g of AcematHK440 (average particle size: 7 μm, manufactured by Degussa) was used instead of the matting agent OK-500 in Example 2. The coating composition and various physical properties are shown in Table 1.

Example 10
A paint was prepared in the same manner as in Example 2 except that 7 g of polyurethane particles (Art Pearl, C-800BK, average particle size = 6 μm, manufactured by Negami Industrial Co., Ltd.) were used. Table 2 shows the paint composition and various physical properties.

Example 11
A 2 L autoclave sufficiently substituted with nitrogen gas and dried was charged with 175 g of ADEKA polyether G-700 (manufactured by Asahi Denka Kogyo Co., Ltd., glycerin PO adduct, hydroxyl value 225 mg / KOHg) and 101 g of hexamethylene diisocyanate, and 120 ° C. And reacted for 20 hours. Thereafter, unreacted hexamethylene diisocyanate was removed under reduced pressure, and then toluene was added to obtain a compound (I) having a nonvolatile content of 90%. 970 g of water was charged into a separable flask equipped with a 2 L stirrer, and 30 g of Hemetroze 90SH-100 (manufactured by Shin-Etsu Chemical Co., Ltd .; methylcellulose) was dissolved therein to prepare a dispersion medium. A solution obtained by diluting 250 g of the compound (I) with 87 g of toluene was added to the dispersion medium while stirring at 1000 rpm to prepare a suspension. With continuous stirring, the suspension was heated to 60 ° C., reacted for 1.5 hours, cooled to room temperature, separated into solid and liquid, thoroughly washed with water, dried at 70 ° C. for 20 hours, and an average particle size of 4 μm. Urethane particles (beads 1) were obtained. A coating material was prepared in the same manner as in Example 2 except that the polyurethane particles synthesized by the above method were used in place of the polyurethane particles in Example 10. Table 2 shows the paint composition and various physical properties.

Example 12
A coating material was prepared in the same manner as in Example 2 except that 7 g of polyurethane particles (Art Pearl, C-400BK, average particle size = 14 μm, manufactured by Negami Industrial Co., Ltd.) were used. Table 2 shows the paint composition and various physical properties.

Example 13
A coating material was prepared in the same manner as in Example 2 except that 4 g of polyurethane particles (Art Pearl, C-800BK, average particle size = 6 μm, manufactured by Negami Industrial Co., Ltd.) were used. Table 2 shows the paint composition and various physical properties.

Example 14
A paint was prepared in the same manner as in Example 2 except that 10 g of polyurethane particles (Art Pearl, C-800BK, average particle size = 6 μm, manufactured by Negami Industrial Co., Ltd.) were used. Table 2 shows the paint composition and various physical properties.

Comparative Example 1
Instead of the polycarbonate diol of Example 1, the polycarbonate diol-5 prepared in Production Example 5 (PCDL-5: 2-methyl-1,3-propanediol and 1,4-butanediol were mixed at a molar ratio of 95/5. A paint was prepared in the same manner as in Example 1, except that the number average molecular weight 2000) was used with the polycarbonate diol obtained by polymerization. Table 3 shows the coating composition and various physical properties.

Comparative Example 2
Polycarbonate diol-6 (PCDL-6: obtained by copolymerizing 2-methyl-1,3-propanediol and 1,4-butanediol at a molar ratio of 20/80 instead of the polycarbonate diol of Example 1 A paint was prepared in the same manner as in Example 1 except that the polycarbonate diol was used and the number average molecular weight was 2000). Table 3 shows the coating composition and various physical properties.

Comparative Example 3
Polycarbonate diol-7 (PCDL-7: obtained by copolymerizing 2-methyl-1,3-propanediol and 1,4-butanediol in a 50/50 molar ratio instead of the polycarbonate diol of Example 1 A paint was prepared in the same manner as in Example 1 except that the polycarbonate diol was used with a number average molecular weight of 500). Table 3 shows the coating composition and various physical properties.

Comparative Example 4
Polycarbonate diol-8 (PCDL-8: obtained by copolymerizing 2-methyl-1,3-propanediol and 1,4-butanediol in a 50/50 molar ratio instead of the polycarbonate diol of Example 1 A paint was prepared in the same manner as in Example 1 except that the number average molecular weight was 4000). Table 3 shows the coating composition and various physical properties.

Comparative Example 5
Instead of the polycarbonate diol of Example 1, the polycarbonate diol-9 produced in Production Example 9 (PCDL-9: 1,5-pentanediol and 1,6-hexanediol were copolymerized at a molar ratio of 50/50. A coating material was prepared in the same manner as in Example 1 except that the obtained polycarbonate diol had a number average molecular weight of 2000). Table 3 shows the coating composition and various physical properties.

Comparative Example 6
In the same manner as in Example 2, except that 5 g of Quattron PL-2 (particle size: 0.02 μm, solid content: 20%, manufactured by Fuso Chemical Industries) was used in place of the matting agent OK-500 of Example 2. A paint was made. Table 3 shows the formulation of paint and its physical properties.

Comparative Example 7
A coating material was prepared in the same manner as in Example 2 except that 5 g of silica 2 (particle size: 30 μm) was used instead of the matting agent OK-500 of Example 2. Table 3 shows the formulation of paint and its physical properties.

Comparative Example 8
A coating material was prepared in the same manner as in Example 2 except that 1 g of the matting agent OK-500 of Example 2 was used. Table 3 shows the formulation of paint and its physical properties.

Comparative Example 9
A coating material was prepared in the same manner as in Example 2 except that 25 g of the matting agent OK-500 of Example 2 was used. Table 3 shows the formulation of paint and its physical properties.

Claims (3)

(A) a polyisocyanate compound having at least two or more isocyanate groups in one molecule;
(B) It consists of repeating units of the following formulas (1) and (2), and the ratio of (1) and (2) is (1) / (2) = 90/10 to 30/70 (molar ratio). An aliphatic polycarbonate diol having a number average molecular weight of 550 to 3500 and having a hydroxyl group as a terminal group ;

(C) a silica-based matting agent having an average particle size of 0.1 to 10 μm; and
(D) A curable coating composition containing polyurethane particles having an average particle diameter of 2 to 20 [ mu] m as an essential component, wherein the polyisocyanate compound (a) comprises biuret type, allophanate type, uretidine dione At least one selected from the group consisting of a diisocyanate derivative of type or isocyanurate type and a polyhydric alcohol adduct type polyisocyanate compound, and the silica matting agent (c) is used for the curable coating 3 to 30% by mass in the total solid content of the composition, and 0 to 30% by mass (excluding 0% by mass) of the polyurethane particles (d) in the total solid content of the curable coating composition object. The curable coating composition according to claim 1, wherein the polyisocyanate compound (a) has at least 2.5 or more isocyanate groups in one molecule. The curable coating composition according to claim 1, further comprising 0 to 90% by mass of an inert organic solvent (excluding 0% by mass).