JP2003105166A - Resin composition and coating composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating resin composition which has no problem of damaging the old coating or the material to be coated, simultaneously, can coat thick by single coating and, in addition, has good adhesion, and excels in lifting-resistant properties/barrier properties on recoating. SOLUTION: The coating composition comprises a hydroxyl group-containing vinyl polymer, a glycerin ester of a 6-20C fatty acid, and a nonpolar organic solvent having an aniline point of 10-70 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, and more specifically, it does not attack an old coating film or a material to be coated, enables high solidification, has excellent adhesiveness, and improves workability and work environment. TECHNICAL FIELD The present invention relates to a resin composition and a coating composition that can be improved.

[0002]

2. Description of the Related Art Acrylic urethane paints are dry at room temperature and, in addition, they have very good coating properties such as weather resistance, solvent resistance, water resistance and stain resistance. It has been widely used in fields such as automobile repair.

However, the acrylic urethane paint is
Since it is diluted with an organic solvent such as acetic acid esters, ketones, and aromatic hydrocarbons, which has a strong dissolving power and is highly toxic, it may seriously hinder the working environment during coating. Also, when such acrylic urethane paint is applied, repainted or repaired on a base material that is not resistant to solvents such as automobile repairs, building exteriors, roofs, plastics, etc. There is also a problem that it damages the underlying coating film to be applied. Further, when the acrylic urethane paint is further overcoated, lifting may occur. As described above, in the conventional acrylic urethane coating, there may be a big obstacle in practical use in terms of working environment and workability, and it is strongly desired to reduce the amount of volatile organic solvent used and improve workability. ing.

Therefore, in order to improve the work environment and the problem of attacking the old coating film and the base coating film, in place of the volatile organic solvent, an aliphatic hydrocarbon solvent such as mineral spirit (non-polar organic solvent) is used. We are developing a weak solvent type acrylic / urethane paint mainly composed of solvent.
-215662, JP-A-7-48518 and the like are proposed.

However, JP-A-62-215662
In the resin composition for paints disclosed in the publication, the viscosity of the paint becomes high, so that a paint with a high solid content cannot be obtained, and a large amount of hydroxyl group is added to the polymer component in order to improve the crosslinkability. Introduced into No. 1), the solubility of the polymer in a solvent was lowered, and it was practically impossible to produce a highly crosslinkable coating material. Therefore, the coating cannot be thickly applied by one-time application, and the barrier property (solvent resistance) of the applied coating film cannot be said to be sufficient.

Further, the coating composition disclosed in JP-A-7-48518 enables thick coating by one coating, but since the resin composition is a dispersion, the crosslinking efficiency is poor, It is not possible to obtain a paint with sufficient adhesion.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and its purpose is to use any substrate, primer, old coating film, substrate Not only can it be applied on the coating film, it can be applied thickly by one-time application.
It is an object of the present invention to provide a resin composition and a coating composition which have good adhesion and are excellent in lifting resistance and barrier properties during repeated coating.

[0008]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have conducted various studies on the improvement of the solubility between the hydroxyl group-containing vinyl polymer and the nonpolar organic solvent in the resin composition, and as a result, specific When glycerin ester of fatty acid is used, the solubility of the polymer and the non-polar organic solvent can be dramatically improved even if the number of hydroxyl groups in the hydroxyl group-containing vinyl polymer is improved, and sufficient crosslinkability is also obtained. I found that I could be. Then, by combining such a resin composition and a polyisocyanate soluble in a non-polar organic solvent, high solidification is possible without damaging the old coating film / primary coating film or the coating material, and The inventors have found that a coating composition that enables thick coating by coating and that has good adhesion, lifting resistance and barrier properties can be obtained, and completed the present invention.

That is, the resin composition of the present invention comprises (A)
Hydroxyl group-containing vinyl polymer, (B) C6-18 fatty acid glycerin ester and (C) aniline point 10
It contains a non-polar organic solvent at ˜70 ° C.

Further, the coating composition of the present invention contains the above-mentioned resin composition and a polyisocyanate compound soluble in a non-polar organic solvent, and the isocyanate group in the polyisocyanate compound is 0 relative to 1 equivalent of the hydroxyl group of the resin composition. .5-2.0
It is characterized in that it is contained in such a ratio as to be (equivalent ratio).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION First, the hydroxyl group-containing vinyl polymer contained in the resin composition of the present invention will be described. Such a hydroxyl group-containing vinyl polymer is used to obtain a crosslinking point between an isocyanate compound and a resin composition when forming a coating composition, and if the polymer itself has a hydroxyl group, There is no limit. For example, a product obtained by polymerizing a vinyl monomer containing a hydroxyl group can be used.

Here, as typical examples of the vinyl monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate Or hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as polyethylene glycol mono (meth) acrylate and the like;
Vinyl monomers added with ε-caprolactone (Placcel FA monomer and FM monomer manufactured by Daicel Chemical Industries Ltd.); methylol group-containing compounds such as N-methylol acrylamide; hydroxyethyl vinyl ether and the like. Among these, it is preferable to use 2-hydroxypropyl (meth) acrylate as a monomer component. In addition, the above-mentioned vinyl monomer containing a hydroxyl group may be used alone or in combination of two or more kinds.

As described above, the hydroxyl group-containing vinyl polymer of the present invention is used for obtaining a crosslinking point with an isocyanate compound when forming a coating composition. It is preferably in the range of 5 to 150 mgKOH / g (polymer solid content), particularly 30 to 70 mgKOH / g (polymer solid content). 5mgKOH /
If it is less than g (polymer solid content), the crosslinking density is too small,
Also, generally 50 mgKOH / g (polymer solid content)
When it is above, the polarity becomes high and it becomes difficult to dissolve in a nonpolar organic solvent. However, when the glycerin ester of the specific fatty acid in the present invention is used, there is no problem even if the hydroxyl value of the polymer is 50 mgKOH / g (polymer solid content) or more, and 150 mgKOH / g (polymer solid content). ) It is possible to obtain a resin composition in a good state as long as it is below.

Further, the hydroxyl group-containing vinyl polymer of the present invention comprises at least one vinyl monomer copolymerizable with the above-mentioned hydroxyl group-containing vinyl monomer.
It may be a copolymer with a hydroxyl group-containing vinyl monomer. Here, as the vinyl-based monomer copolymerizable with the hydroxyl group-containing vinyl-based monomer, (1) aromatic vinyl-based monomers such as styrene, α-methylstyrene, pt-butylstyrene, and vinyltoluene: (2) Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-
(Meth) acrylates such as propyl (meth) acrylate, lauryl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or alkoxyalkyl (meth) acrylate; maleic acid, fumaric acid or itaconic acid Such diesters of unsaturated dicarboxylic acids and monohydric alcohols; vinyl acetate, vinyl benzoate, vinyl esters, fluorine-containing acrylic monomers, perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or Ni -(Per) fluoroalkyl group-containing vinyl esters such as propyl perfluorooctane sulfonamide ethyl (meth) acrylate, vinyl ethers, (meth) acrylates or unsaturated poly (vinyl ether) s. Fluorine-containing compounds such as boric acid esters; or vinyl-based monomers having no functional group such as olefins such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride: (3) Glycidyl Hydroxyl group such as (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, (meth) allyl glycidyl ether or the α, β-ethylenically unsaturated carboxylic acids or mono-2- (meth) acryloyloxymonoethyl phthalate Containing vinyl monomers: (4) Silicon-based monomers such as vinylethoxysilane and γ-methacryloxypropyltrimethoxysilane: (5) 2- (meth) acryloyloxyethyl acid phosphate, dibutyl (2- (meth) acryl) Loyloxyethyl) ho Phosphate-based monomers such as sulfate: (6) Amide-group-containing vinyl-based monomers such as (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide: (7) Dimethylaminoethyl (meth) Acrylate, dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate, (8) n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl ( (Meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth)
Esters of (meth) acrylic acid such as acrylate and monohydric alcohol having 4 to 8 carbon atoms; dibutylmalate, di-2-ethylhexylmalate, dibutylfumarate,
Di-2-ethyl fumarate, dibutyl itaconate, di-2-ethylhexyl itaconate, etc. Diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid with monohydric alcohols having 4 to 8 carbon atoms Vinyl-based monomers having a side chain alkyl having 4 to 8 carbon atoms: and the like.

The amount of each of the vinyl monomer components (1) to (8) described above depends on the balance with the amount of the other components, copolymerizability, or the amount of the non-polar organic solvent to be combined with the produced polymer. Solubility, painting workability, gloss, flexibility,
Considering various physical properties of coating film such as hardness, weather resistance, drying property, solvent resistance, abrasion property, compatibility, dilution property, chemical resistance, resin viscosity, pigment dispersibility, adhesion property, pot life, glass transition point, etc. However, it may be determined in the range of 0 to 49% by weight with respect to the total amount of monomers constituting the hydroxyl group-containing vinyl polymer. In addition,
When using an aromatic vinyl-based monomer, the amount used should be 40% by weight or less, particularly 20% by weight or less, based on the total amount of monomers, from the viewpoint of weather resistance and yellowing resistance of the resulting coating film. Is preferred.

Further, among the above-mentioned monomers, vinyl monomers having a side chain alkyl having 4 to 8 carbon atoms, particularly n-butyl methacrylate and i-butyl methacrylate, from the viewpoint of solubility in a non-polar organic solvent. , T-butyl methacrylate or cyclohexyl (meth) acrylate is preferably copolymerized with the above-mentioned vinyl monomer having a hydroxyl group. In addition, you may copolymerize with a hydroxyl-containing vinyl-type monomer using 2 or more types of vinyl-type monomers which have these C4-C8 side chain alkyl. From the viewpoint of solubility in non-polar organic solvent, stain resistance of cured coating film, solvent resistance, hardness, drying property, blocking resistance, etc., the amount used is 10 to 40% by weight based on the total amount of monomers. %, Particularly preferably 20 to 40% by weight.

The polymerization conditions for the hydroxyl group-containing vinyl polymer of the present invention may be in accordance with ordinary methods, for example, in the ordinary polymerization method, the solvent has an aniline point of 10 to 70.
Examples include a method of polymerizing the above-mentioned monomer using a nonpolar organic solvent at ℃. Moreover, as an initiator at the time of polymerization, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t-butyl perbenzoate, tert-butyl perbenzoate (TBP)
B), t-butyl hydroperoxide (TBHP
O), di-t-butyl peroxide (DTBPO), cumene hydroperoxide (CHP), and other initiators can be used.

In the conventional resin composition for coating material, the glass transition point (Tg) of the hydroxyl group-containing vinyl polymer is -30.
If it is less than ℃, stain resistance, solvent resistance, hardness, drying property, blocking resistance, etc. of the cured coating film will be poor. On the other hand, if it is 50 ° C or higher, the cured coating film will be hard and brittle, and cracks will easily occur. It is considered to be unfavorable because the elongation, bending, impact resistance, Erichsen, etc. of the film also decrease. Therefore, in the resin composition containing only the above-mentioned polymer as the polymer component, it is preferable that the Tg of the polymer is within the range of -30 to 50 ° C, but in the present invention, as described below, Since it contains the glycerin ester of fatty acid of, the Tg is 80 in addition to that of -30 to 50 ° C.
Even if a hydroxyl group-containing vinyl polymer having a temperature of not higher than 0 ° C. is used, the above problem does not occur and a good coating film can be obtained.

In the hydroxyl group-containing vinyl polymer of the present invention, if the number average molecular weight is less than 4000,
The coating film physical properties such as elongation, weather resistance and hardness are insufficient.
When it is 0000 or more, the feeling of fleshness, spray workability, coating appearance, etc. deteriorate, so the number average molecular weight is 4000-2.
It is preferable to use 0000, and more preferably 6000 to 12000. Furthermore, when the weight average molecular weight / number average molecular weight ratio (Mw / Mn) is less than 1.8, pigment dispersibility and coating film physical properties are often insufficient, and when the ratio is 10 or more, a flesh feeling and a spray are obtained. Since inconvenience may occur in terms of workability and coating film appearance pot life, it is preferable that Mw / Mn = 1.8 to 10,
The range is more preferably 2 to 6. The molecular weight of the hydroxyl group-containing vinyl polymer referred to herein is a value calculated as a polystyrene-equivalent molecular weight using GPC (carrier: THF).

The glycerin ester of fatty acid in the present invention means a glycerin triester, a glycerin diester or a glycerin monoester of a fatty acid, preferably a fatty acid glycerin triester as a main component. Further, the fatty acid component in the present invention has 6 to 20 carbon atoms, preferably 14 to 18 carbon atoms, and more preferably 16 to 18 carbon atoms.

The fatty acid component may be saturated fatty acid such as palmitic acid, stearic acid, myristic acid, arachidic acid, capric acid, caprylic acid, caproic acid, oleic acid, linoleic acid, linoleic acid, eleostearine. An unsaturated fatty acid such as an acid or ricinoleic acid may be used. The glycerin ester of fatty acid of the present invention may contain only one type of fatty acid component,
It may contain two or more kinds of fatty acid components. In the present invention, those containing at least one kind of fatty acid selected from oleic acid, linoleic acid and stearic acid as a fatty acid component are preferable.

The fatty acid glycerin ester of the present invention may itself contain a hydroxyl group, in which case it functions as a coating film forming cross-linking component by reacting with a curing agent at the time of forming a coating film, Gives good coating performance.

Examples of preferable glycerin esters of fatty acids used in the present invention include naturally occurring fats and oils, and specifically, castor oil, linseed oil, enoki oil,
Examples thereof include safflower oil, unripe oil, soybean oil, tall oil, cottonseed oil, and coconut oil. Among these, castor oil containing a hydroxyl group (refined castor oil, modified castor oil) is particularly preferable from the viewpoint of crosslinkability with a curing agent and solubility between a polymer and a solvent.

The glycerin ester of a fatty acid having 6 to 20 carbon atoms in the present invention may be preliminarily mixed at the time of polymerizing the hydroxyl group-containing vinyl polymer, or may be mixed after the polymerization.

The amount of the fatty acid glycerin ester used in the present invention influences the stain resistance, solvent resistance, hardness, drying property, blocking resistance, toughness, etc. of the cured coating film, as in the case of the hydroxyl group-containing vinyl polymer. Exert. Therefore, depending on the performance of the cured coating film based on the combination with the hydroxyl group-containing vinyl-based polymer to be used, the amount used is preferably in the range of 1 to 50% by weight based on the entire hydroxyl-containing vinyl-based polymer, and more preferably Is 5 to 20% by weight. When used in such a range, it is possible to obtain a good coating film that is very well balanced in terms of coating film performance.

Here, in the resin composition for coating composition of the present invention, it is desirable that the fatty acid glycerin ester component does not add to the monomer component used for the vinyl polymer having hydroxyl group. When the addition reaction between the fatty acid glycerin ester component and the hydroxyl group-containing vinyl-based monomer occurs, the viscosity of the composition increases, and further, the solubility of the hydroxyl group-containing vinyl polymer in the nonpolar organic solvent may decrease. There is. That is, since the glycerin ester of the fatty acid of the present invention acts as a diluent and a compatibilizer in a state before coating, it is possible to suppress an increase in viscosity of the resin composition, and also to contain a hydroxyl group for a nonpolar organic solvent. The solubility of vinyl polymerization resistance can be improved.

Subsequently, the nonpolar organic solvent of the present invention means a nonpolar aliphatic hydrocarbon having an aniline point in the range of 10 to 70 ° C., preferably 15 to 65 ° C. and having a relatively weak dissolving power.
It is a naphthene-based hydrocarbon-based organic solvent, and these can be used alone or in admixture of two or more. As a typical example, "HAWS" (manufactured by Shell:
Aniline point = 15 ° C.), “Swazol 310” (Maruzen Oil Co., Ltd .: aniline point = 16 ° C.), “K Solvent” (Nippon Oil Co., Ltd .: aniline point = 37 ° C.) “LAWS” (Shell, Inc .: aniline point) = 44 ° C), "A Solvent" (manufactured by Nippon Oil Co., Ltd .: aniline point = 45 ° C),
O. 6 "(manufactured by Exxon: aniline point = 43 ° C)," Essonaphtha NO. 5 "(manufactured by Exxon: aniline point = 5)
5 ° C.), “Pegasol 3040” (manufactured by Mobil: aniline point = 55 ° C.), mineral spirits (aniline point =
Petroleum hydrocarbon organic solvents such as 52 ° C.); alicyclic hydrocarbon organic solvents such as methylcyclohexane (aniline point = 40 ° C.) and ethylcyclohexane (aniline point = 44 ° C.); terpen oils such as turpentine oil And so on.

The content of the non-polar organic solvent in the resin composition is generally in the range of 5 to 95% by weight based on the resin composition from the viewpoint of maintaining the fluidity required as a paint. . However, in order to obtain a constant film thickness after coating film formation, the content of the nonpolar organic solvent is preferably 70% by weight or less, more preferably 40 to 60% by weight, based on the resin composition. .

The method for producing the resin composition of the present invention is not particularly limited and may be a general method for producing an acrylic resin. In addition, glycerin ester of fatty acid,
It may be added during the polymerization of the monomer or may be added to the polymer after the polymerization.

The coating composition of the present invention can be prepared by blending the above-mentioned resin composition of the present invention with a polyisocyanate compound as a curing agent.

The polyisocyanate compound used as a curing agent is not particularly limited, but when it is not sufficiently soluble in the non-polar organic solvent of the present invention, it is added to the resin composition for coating composition. However, there is a possibility that the polyisocyanate compound is separated and the desired curing performance cannot be obtained. Therefore, in the present invention, it is necessary to use a polyisocyanate compound having sufficient solubility in a nonpolar organic solvent.

Typical examples of such a polyisocyanate compound include Burnock DN-990, D
N-990S, DN-991, DN-991S, DN-
992 (manufactured by Dainippon Ink Industry Co., Ltd.), Desmodur Z-4370 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate TSA-100, TSS-100, TSE-1.
00 (manufactured by Asahi Kasei Kogyo Co., Ltd.) and the like.

With respect to the amount of the polyisocyanate compound compounded, the hydroxyl group (OH) 1 contained in the resin composition is
Use within a range such that the ratio of the isocyanate group (NCO) of the polyisocyanate compound to the equivalent (hereinafter, sometimes abbreviated as "OH / NCO ratio") is 0.5 to 2.0 (equivalent ratio). Is preferred. Hydroxyl group (OH)
When the compounding ratio of the isocyanate group (NCO) to 1 equivalent is less than 0.5 equivalent, the crosslinking tends to be insufficient, and it is difficult to obtain the effect of using such a polyisocyanate curing agent, while the compounding ratio is 2 If it is larger than 0.0, there may be a problem of foaming when the coated surface having a high water content is coated, and it is not desirable in view of drying property or coating cost.

In the coating composition of the present invention, a pigment dispersant, a leveling agent, an ultraviolet absorber, a light stabilizer, a curing accelerator, etc., which are generally known in the art, are generally used in conventional amounts. be able to. Further, as long as it is compatible with and soluble in the coating resin composition of the present invention, a plasticizer, another resin, or a copolymer may be used in combination for the purpose of improving performance.

The coating composition of the present invention can be used as a so-called enamel coating by mixing and kneading it with pigments or mixing dispersed pigments and processed pigments. It is also possible to use it as a so-called clear paint without using any kind. In addition, polar organic solvents for coating materials known in the art may be used within a range that does not impair the object of the present invention, but in order not to impair the effects of the present invention as much as possible, 35% of all solvents are used. weight%
Below, it should desirably be limited to 0 to 20% by weight. Examples of such polar organic solvent include ethyl acetate,
Ester solvent such as butyl acetate, methyl ethyl ketone,
Examples thereof include ketone-based solvents such as methyl ishibutyl ketone, ether-based solvents such as butyl cellosolve acetate, and aromatic solvents such as toluene and xylene.

The resin composition of the present invention has 6 carbon atoms.
Since the glycerin ester of fatty acid of 20 to 20 is included, the solubility of the hydroxyl group-containing vinyl polymer and the nonpolar organic solvent can be dramatically improved. Therefore, even if the concentration of the hydroxyl group in the polymer is increased, the solubility of the polymer in the nonpolar solvent is not decreased, and a highly crosslinkable coating composition can be prepared. Further, in the resin composition for paints of the present invention, the glycerin ester of a fatty acid having 6 to 20 carbon atoms also serves as a diluent, so that even when it is used as a paint, an increase in viscosity can be suppressed, resulting in a high viscosity. It becomes possible to make a solid paint.

A coating composition obtained by blending the resin composition of the present invention and a polyisocyanate compound soluble in a non-polar organic solvent has high adhesiveness due to its high cross-linking property, and has a good adhesive property during repeated coating. Has excellent lifting resistance and barrier properties. Moreover, since the resin composition for coating material of the present invention can have a high solid content, it is possible to perform thick coating by one-time coating. Furthermore, since the coating composition of the present invention uses a non-polar organic solvent, it has little toxicity and has the effect of not attacking the old coating film or the coating material. Furthermore, in the coating of the coating composition of the present invention, the so-called known means such as a spray, a brush or a roller can be applied as they are because they have the above-mentioned characteristics. Further, as the curing conditions of the coating composition in the present invention, known conventional conditions such as room temperature curing drying and heat curing drying can be adopted.

As described above, according to the present invention, the working environment can be remarkably improved as compared with the conventional case where a highly toxic polar solvent is used, and in terms of performance, any substrate, primer or old coating film can be used. It is possible to obtain a resin composition for coating and a coating composition which can be applied on the top and can be thickly applied by one application. In addition, the coating composition of the present invention has excellent workability, and further has excellent effects such as excellent adhesion and excellent lifting resistance and barrier property during repeated coating. As described above, the resin composition and the coating composition of the present invention can be used as a two-pack type coating material which is very suitable for the fields of construction, automobile repair, industrial machinery, metal, and the like.

[0039]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. All parts and% shown below are based on weight unless otherwise specified.

First, the viscosity of the resin compositions used in the following examples and comparative examples, and the method for measuring the hydroxyl value, acid value and molecular weight of the hydroxyl group-containing vinyl polymer will be described.

(Viscosity of Resin Composition) The viscosity of the resin composition is measured by a JIS K method using a B-type viscometer (Tokyo Keiki Co., Ltd.).
It was measured according to 5400 4.5.3. That is,
First, add the resin composition so that bubbles do not enter the sample container, then insert a thermometer into the resin composition, so that the mercury ball of the thermometer is located in the center of the resin composition. The sample container was sealed. Then, the resin composition was kept in a constant temperature bath adjusted to 25 ° C. so that the temperature of the resin composition was 25 ° C. ±
After confirming that the temperature is 0.2 ° C, remove the thermometer and
Viscosity of a resin composition [mPa · s, 25
C] was calculated.

(Acid Value of Vinyl Polymer Having Hydroxyl Group) The acid value of the vinyl polymer having hydroxyl group is determined according to JIS K 0070.
It measured according to 7.1. That is, 2 to 3 g (solid content) of a hydroxyl group-containing vinyl polymer is precisely weighed in a 300 ml conical beaker, and 50 ml of a mixed solution of alcohol and benzene (alcohol: benzene = 1: 1) is added thereto to dissolve the polymer. Let After dissolution, 4-5 as an indicator
Add a drop of 1% phenolphthalein and add 0.1N-Na
Titration was performed with OH, and the point where the red color continued for 30 seconds was regarded as the end point. A blank test was conducted in the same manner, and the following formula (1)
Therefore, the acid value of the hydroxyl group-containing vinyl polymer (mgKOH /
g, solid) was calculated.

Acid value = [(A−B) × 56.1 × f × 0.1] / E (1) (A: 0.1 required for titration of hydroxyl group-containing vinyl polymer)
Ml of N-NaOH, B: 0.1 required for blank titration.
Ml of 1N-NaOH, f: factor of 0.1N-NaOH, E: collection amount of hydroxyl group-containing vinyl polymer (g))

(Hydroxyl value of hydroxyl group-containing vinyl polymer)
The hydroxyl value of the hydroxyl group-containing vinyl polymer is JIS K
It was measured according to 7.3. That is, 2 to 3 g (solid content) of a hydroxyl group-containing vinyl polymer was precisely weighed in an Erlenmeyer flask in which 300 ml were laid, and 10 ml of an acetylating agent (pyridine: acetic anhydride = 4: 1) was added thereto and left for 1 minute. After putting the boiling stones and attaching the rising tube to the Erlenmeyer flask, the acetylation reaction was carried out for 30 minutes on a hot plate at about 120 ° C. while shaking the Erlenmeyer flask frequently. After the acetylation was completed, the mixture was naturally cooled, and then cooled with ice water with the rising tube attached. Wash the riser and Erlenmeyer flask slides with 25 ml of pyridine (cooling), then 50 ml
The riser and flask slides were washed with distilled water (cooling). The rising tube was removed, 4 to 5 drops of 1% phenolphthalein was added as an indicator, titration was carried out with 1N-KOH, and the point where red color continued for 30 seconds was taken as the end point. A blank test was conducted in the same manner, and from the following formula (2), the hydroxyl value of the hydroxyl group-containing vinyl polymer (mgKOH / g, sol
id).

Hydroxyl value = [{(BA) × 56.1 × f} × 1 / E] + acid value (2) (A: 1N− required for titration of hydroxyl group-containing vinyl polymer)
KOH ml, B: 1N-KO required for blank titration
Ml of H, f: factor of 1N-KOH, E: amount of hydroxyl group-containing vinyl polymer collected (g), acid value: value determined by the above formula (1))

(Molecular Weight of Vinyl Polymer Having Hydroxyl Group) The average molecular weight (converted to standard polystyrene) of the vinyl polymer having hydroxyl group was determined by gel permeation chromatography (GPC) under the following conditions. Column: Tosoh Corp. TSKgelSuperH20
00, 3000, 4000, 5000, carrier: THF, GPC device: HLC-8120GPC manufactured by Tosoh Corporation, detector: differential refractometer, data processing device: SC-8020 manufactured by Tosoh Corporation.

(Synthesis of Resin Composition)

Example 1 303.3 parts of A solvent (manufactured by Nippon Oil Co., Ltd .: aniline point = 45 ° C.) as a nonpolar organic solvent was placed in a 4-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe. Then, 100 parts of castor oil, 200 parts of i-butyl methacrylate as a monomer component, 30 parts of 2-hydroxypropyl acrylate, and 20 parts of cyclohexyl acrylate were charged, and the temperature was raised to 120 ° C. There, 200 parts of i-butyl methacrylate, 3
A mixture of 0 parts 2-hydroxypropyl acrylate, 20 parts cyclohexyl acrylate, 4.5 parts benzoyl peroxide and 50 parts A solvent was added dropwise over 3 hours. At the same temperature after the dropping is completed, 1
Reacted for hours.

Further, a mixture of 50 parts of A solvent and 0.5 parts of benzoyl peroxide was added dropwise over 1 hour. After the dropping was completed, the reaction was carried out at the same temperature for 3 hours. Non-volatile content is 60.0% and viscosity is 7,000 mPa.
Transparent castor oil-containing vinyl-based monomer copolymer weight of s, 25 ° C, hydroxyl value of 60 mgKOH / g (solid content), acid value of 0.5 mgKOH / g (solid content), molecular weight of Mw = 40000, Mn = 9500 A combined solution was obtained. When the state of the polymer solution after confirming the state of the polymer solution after diluting the obtained polymer solution by 200% and allowing it to stand at 0 ° C. for 5 days, no change in state such as cloudiness or separation was confirmed.

[0049]

Example 2 In a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 304 parts of A solvent (Nippon Petroleum: aniline point = 45 ° C.) as a non-polar organic solvent, and 50 parts of castor oil was charged and the temperature was raised to 120 ° C. 220 parts of n-butyl methacrylate, 250 parts of i-butyl methacrylate, 35 parts of 2-hydroxypropyl acrylate, 40 parts of cyclohexyl acrylate, 5 parts of dimethylaminoethyl acrylate, 5 parts of benzoyl peroxide, and Fifty
A mixture of 1 part A solvent was added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour.

Further, a mixture of 50 parts of A solvent and 1 part of benzoyl peroxide was added dropwise over 1 hour. After the dropping was completed, the reaction was carried out at the same temperature for 3 hours.
Non-volatile content is 60.0%, viscosity is 7,000 mPas,
25 ° C., hydroxyl value 33 mgKOH / g (solid content), acid value 0.3 mgKOH / g (solid content), molecular weight Mw =
A transparent castor oil-containing vinyl-based monomer copolymer solution having 31,000 and Mn = 8300 was obtained. When the state of the polymer solution after confirming the state of the polymer solution after diluting the obtained polymer solution by 200% and allowing it to stand at 0 ° C. for 5 days, no change in state such as cloudiness or separation was confirmed.

[0051]

[Example 3] In a 4-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 303.3 parts of A solvent (manufactured by Nippon Oil Co., Ltd .: aniline point = 45 ° C) was used as a non-polar organic solvent. Then, 100 parts of castor oil, 166 parts of i-butyl methacrylate as a monomer component, 32 parts of 2-hydroxypropyl acrylate, and 2 parts of dimethylaminoethyl acrylate were charged, and the temperature was raised to 120 ° C. 249 parts of i-butyl methacrylate,
A mixture of 48 parts 2-hydroxypropyl acrylate, 3 parts dimethylaminoethyl acrylate, 4.5 parts benzoyl peroxide and 50 parts A solvent was added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour.

Further, a mixture of 50 parts of A solvent and 0.5 parts of benzoyl peroxide was added dropwise over 1 hour. After the dropping was completed, the reaction was carried out at the same temperature for 3 hours. Non-volatile content is 60.0% and viscosity is 15,000 mPa.
-S, 25 ° C, a transparent castor oil-containing vinyl system having a hydroxyl value of 71.6 mgKOH / g (solid content), an acid value of 0.5 mgKOH / g (solid content), a molecular weight of Mw = 60,000 and Mn = 14,000. A monomer copolymer solution was obtained.
When the state of the polymer solution after confirming the state of the polymer solution after diluting the obtained polymer solution by 200% and allowing it to stand at 0 ° C. for 5 days, no change in state such as cloudiness or separation was confirmed.

[0053]

[Comparative Example 1] In a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 256.6 parts of A solvent (manufactured by Nippon Oil Co., Ltd .: aniline point = 45 ° C.) as a non-polar organic solvent. As a monomer component, 200 parts of i-butyl methacrylate, 30 parts of 2-hydroxypropyl acrylate, and 20 parts of cyclohexyl acrylate were charged, and the temperature was raised to 120 ° C. There are 200 copies of i
-Butyl methacrylate, 30 parts 2-hydroxypropyl acrylate, 20 parts cyclohexyl acrylate, 4.5 parts benzoyl peroxide and 40 parts A solvent were added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour.

Further, a mixture of 40 parts of A solvent and 0.5 parts of benzoyl peroxide was added dropwise over 1 hour. After the dropping was completed, the reaction was carried out at the same temperature for 3 hours. Non-volatile content is 60.0% and viscosity is 10,000 mPa.
-Transparent castor oil-containing vinyl monomer having s, 25 ° C, hydroxyl value of 52 mgKOH / g (solid content), acid value of 0.2 mgKOH / g (solid content), and molecular weights of Mw = 45000 and Mn = 23000. A polymer solution was obtained. When the state of the polymer solution after confirming the state of the polymer solution after diluting the obtained polymer solution by 200% and standing at 0 ° C. for 5 days, the polymer solution was clouded and separated.

[0055]

Comparative Example 2 270.6 parts of A solvent (manufactured by Nippon Oil Co., Ltd .: aniline point = 45 ° C.) as a nonpolar organic solvent was placed in a 4-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe. After charging, the temperature was raised to 120 ° C. 220 parts of n-butyl methacrylate, 250 parts of i-butyl methacrylate, 35 parts of 2-hydroxypropyl acrylate, 40 parts of cyclohexyl acrylate, 5 parts of dimethylaminoethyl acrylate, 5 parts of benzoyl peroxide, and A mixture consisting of 50 parts of A solvent was added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour.

Further, a mixture of 50 parts of A solvent and 1 part of benzoyl peroxide was added dropwise over 1 hour. After the dropping was completed, the reaction was carried out at the same temperature for 3 hours.
Non-volatile content is 60.0% and viscosity is 10,000 mPa.
Clear castor oil-containing vinyl-based monomer copolymer weight, s, 25 ° C, hydroxyl value 29 mgKOH / g (solid content), acid value 0.1 mgKOH / g (solid content), molecular weight Mw = 33000, Mn = 18000 A combined solution was obtained. The state of the polymer solution after confirming the state of the polymer solution after diluting the obtained polymer solution by 200% and allowing it to stand at 0 ° C. for 5 days was cloudy.

(Preparation of paint / Preparation of test specimen / Evaluation of physical properties) The resin compositions synthesized in Examples 1 to 3 and Comparative Examples 1 and 2 were made into paint, preparation of test specimens, and evaluation of physical properties of test specimens.
First, 120 parts of each polymer solution of Examples 1 to 3 and Comparative Examples 1 and 2 and Taipaque CR-93 (Ishihara Sangyo Co., Ltd.)
40 parts of rutile-type titanium oxide) was dispersed in a sand mill to obtain a white enamel paint having a PWC (pigment weight concentration) of 40%. Next, Vernock DN-990 (Dainippon Ink and Chemicals, Inc.) as a curing agent was added to the obtained coating material so that the OH / NCO equivalent ratio would be 1.1, and further sprayed with A solvent. After diluting to a proper viscosity, it was spray-painted on a mild steel plate and an aluminum plate.
Then, the following physical properties were evaluated for the coating film cured at room temperature for 2 weeks. The results are shown in Table 1.

(Gloss of coating film) Initial gloss of the coating film surface (60
The specular gloss value was measured using a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. according to the measuring method of JIS K5400.7.6. The higher the value of 60 ° specular gloss, the better the gloss.

(Adhesiveness of coating film) The adhesiveness of the coating film was evaluated by a substrate test (in accordance with the cross-cut test method of JIS K5400 8.5.2.). Specifically, the test piece coated with the coating material was used to make cuts in a grid pattern (25 grids; vertical 5 divisions × horizontal 5 divisions) using a cutter guide with a gap of 4 mm. Next, cellophane tape was adhered so as to cover the entire 25 cross-cuts, and one end of the cellophane tape after the adhesion was held, and the cellophane tape was momentarily peeled off in a direction perpendicular to the coated surface to observe the adhered state of the coating film. In addition, the adhesion state of the coating film is 0 point (the area of the defective portion: 65% or more of the total square area), 2 points (the area of the defective portion: 35 to 65 of the total square area).
%), 4 points (defective area: 15 to 35 of total square area)
%), 6 points (defective area: 5 to 15 of total square area)
%), 8 points (defective area: 5% or less of the total square area) and 10 points (no defective area).

(Lifting resistance of the coating film) Regarding the lifting resistance of the coating film, after cross-cutting the cured coating film with a cutter, spraying the white enamel paint again in the same manner as described above. Painting was performed and the presence or absence of lifting was observed. The observation results were evaluated according to the following three grades. ◯: No change (no lifting occurred) △: Slight lifting occurred some time after coating ×: Large lifting occurred immediately after coating

(Weather resistance of coating film) Regarding the weather resistance of the coating film, JIS K5400 9.8.1 (accelerated deterioration test)
It evaluated according to. In the accelerated test, a change in the coating film was investigated by spraying a mist of water at regular intervals while irradiating light with a sunshine weather meter (SWOM). As a test condition, the temperature inside the tank is 63 with a black panel thermometer.
Adjusted to ± 3 ℃, water injection time is 120 minutes during irradiation 18
Minutes The weather resistance was measured by measuring the 60 ° gloss value of the surface of the test piece 1000 hours after the start of the test and comparing it with the initial 60 ° gloss value of the test piece before the start of the test. The 60 ° gloss value was measured using a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. according to the method for measuring the specular gloss of JIS K5400 7.6 described above.

[0062]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AA051 BE041 BG071 BG081                       BG121 BH021 EH046 EH056                       GH01                 4J034 BA08 CA02 CA04 CB03 CB07                       CC03 CD06 DA01 DB03 DB07                       DP18 DP20 HA01 HA06 QA03                       RA07                 4J038 CC021 CD021 CD101 CD121                       CE051 CF021 CF031 CG141                       CG171 CH121 CL001 DG262                       GA03 JA57 KA03 KA06 MA14                       NA11 NA12 NA23 PB05 PB06                       PB07 PC02

Claims (2)

[Claims] 1. A vinyl polymer having a hydroxyl group (A),
A resin composition containing (B) a glycerin ester of a fatty acid having 6 to 20 carbon atoms and (C) a nonpolar organic solvent having an aniline point of 10 to 70 ° C. 2. A resin composition according to claim 1 and a polyisocyanate compound soluble in the non-polar organic solvent,
A coating composition in which the ratio of the isocyanate group of the polyisocyanate compound to 1 equivalent of the hydroxyl group of the resin composition is 0.5 to 2.0 (equivalent ratio).