JPS59122557A - Coating resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition giving a coating film having excellent adhesivity and gloss, by compounding a specific vinyl copolymer modified with a fatty acid and a vinyl copolymer containing functional group such as carboxyl group. CONSTITUTION:The objective composition is prepared by compounding (A) a fatty acid-modified vinyl copolymer obtained by the addition reaction of (i) 100pts.wt. of a vinyl copolymer containing (beta-methyl)glycidyl group and obtained by the copolymerization of (a) 0-60wt%, preferably 10-50wt% of styrene, (b) 95-3wt% of (beta-methyl)glycidyl (meth)acrylate, and (c) 5-97wt% of a copolymerizable vinyl monomer with (ii) 5-190pts.wt. of a fatty acid having an iodine value of 30-200, with (B) a vinyl copolymer having functional group selected from carboxyl group, phosphate group and/or amino group at a weight ratio (B/A) of 1/99-80/20 (solid basis), and if necessary, adding (C) an amino resin or an isocyanate prepolymer to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for coatings, and more particularly, the present invention relates to a resin composition for coatings, and more particularly, a resin composition comprising a specific fatty acid-modified vinyl copolymer and a functional group-containing vinyl copolymer as essential components, or The present invention relates to a resin composition which also contains a crosslinking agent (C) component and which provides a coating film with excellent adhesion and gloss.

An example of adding a fatty acid to a glycidyl group-containing vinyl copolymer is a method of obtaining an air-curing resin using a drying oil fatty acid. When using polymers, the use of vinyl monomers having functional groups such as carboxyl groups, phosphoric acid groups and/or amino groups, which are said to have a great effect on imparting adhesion to the coating film, is important during polymerization. This is completely unsuitable because it reacts with glycidyl groups and forms a gel, and the reality is that it is impossible to introduce functional groups by such means.

While those with phosphoric acid groups and/or amino groups increase the wettability with pigments, they also have the effect of increasing the gloss of the coating film because the adsorption ability of the pigment to the resin is low. As mentioned above, since vinyl monomers having such functional groups cannot be polymerized, so-called fatty acid-modified vinyl copolymers, in which fatty acids are added to glycidyl group-containing vinyl copolymers, are inevitably inferior in adhesion and gloss. be.

However, as a result of various studies in view of the current situation, the present inventors have discovered a resin composition for paint that has excellent adhesion and gloss, as well as other physical and chemical properties. The present invention has now been completed.

That is, the present invention contains 00 to 60% by weight, preferably 10 to 50% by weight of styrene, and glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate and/or β-methylglycidyl methacrylate [hereinafter, when these are collectively referred to as ( It is abbreviated as β-methyl)glycidyl (meth)acrylate. ]95～
Glycidyl obtained by copolymerizing 6% by weight, preferably 70 to 5% by weight, and 5 to 97% by weight, preferably 85% by weight of other vinyl monomers that can be copolymerized with these monomers. and/or β-methylglycidyl group [hereinafter, when collectively referred to as (β-methyl)glycidyl group, it is abbreviated as (β-methyl)glycidyl group. ] A fatty acid-modified vinyl copolymer (A) obtained by adding a fatty acid having an iodine value of 30 to 200 to 100 parts by weight of the vinyl copolymer containing the polyester, selected from the group consisting of a carboxyl group, a phosphoric acid group, and an amine group. and a vinyl copolymer (B) having at least one functional group in a solid content weight ratio of B)/(A) = 1799 to 80/.
The present invention provides a resin composition for coating, which is mixed in a ratio of 20 and further contains an amino resin or an incyanate prepolymer (C), if necessary.

Since the composition of the present invention is a mixture of a fatty acid-modified vinyl copolymer (A) and a vinyl copolymer having a trifunctional group (Bl), it provides a coating film with excellent layer properties and gloss. Furthermore, if necessary, amino resin or incyanate prepolymer (C) can also be blended, making it possible to create a three-dimensional structure, resulting in a structure with excellent physical and chemical properties. It provides a coating film.

Here, representative fatty acids K are those obtained from natural oils such as linseed oil, tall oil, safflower oil, soybean oil, castor oil, rice bran oil, dehydrated castor oil or Chinese tung oil, and those obtained from "PAMOLYN". )
There are synthetic fatty acids such as ``200'' and ``lol'' (products of Percules, Inc., USA), which can be used alone or in combination of two or more, with an iodine value of 60 to 20.
It is sufficient to keep the iodine value within the range of 0. By doing so, it is possible to prevent negative effects such as yellowing of the coating film when using a high iodine value, and conversely improve advantages such as hardenability. Therefore, it is necessary to take these points into account when selecting and deciding on an appropriate basis.

When the amount of the fatty acid used is less than 5 parts by weight based on 100 weight parts of the (β-methyl)glycidyl group-containing vinyl copolymer, the effect of fatty acid modification on the flexibility and hardness of the coating film is small. Therefore, the effect of the present invention cannot be expected,
On the other hand, when using a high iodine value material, even if the amount exceeds 190 parts by weight, crosslinking by oxidative polymerization of the unsaturated bonds,
Furthermore, due to the crosslinking by the crosslinking agent component (C), the resulting coating film has poor flexibility and becomes brittle, making it impossible to put it into practical use.

In addition, when mixing saturated fatty acids to reduce the iodine value, due to the coexistence of unsaturated bonds, even if crosslinking is performed using the curing agent component (C), the uneven distribution of crosslinking points will result in poor hardness and flexibility. It becomes difficult to simultaneously satisfy both properties, and the overall coating film performance is biased to one side, so such a measure is not unreasonable.

If styrene of more than 60 TLIjk% is used as the above-mentioned (β-methyl)glycidyl group-containing vinyl copolymer (B), the resulting copolymer (A) will have poor weather resistance. The appropriate amount of styrene used is within 60% by weight, preferably in the range of 10 to 50% by weight, and (β-methyl)glycidyl (meth)
Since the (β-methyl)glycidyl group of acrylate reacts with fatty acids, the amount of the monomer used is determined depending on the amount of fatty acid used, but the reaction rate and residual (β-methyl) glycidyl group reacts with fatty acids.
-Methyl)glycidyl groups on the coating film, a range of 1.0 to 1.25 equivalents of (β-methyl)glycidyl groups per equivalent of carboxyl group in the fatty acid is preferable, and other Vinyl monomers can be used in amounts ranging from 5 to 97% by weight, preferably up to 85% by weight.

Typical examples of other vinyl monomers copolymerizable with (β-methyl)glycidyl (meth)acrylate and/or styrene include alkyl (meth)acrylates with alkyl groups of C1 to CSS;
Heptamers such as acrylonitrile, perfluoroalkyl groups or fluoroalkyl group-containing vinyl monomers, vinyl chloride or vinyl acetate, and polymers such as alkyd resins or polyester resins having polymerizable unsaturated bonds in the molecule. However, when using such a polymeric material as a monomer, the amount used is such that even if the (β-methyl)glycidyl group in the resulting copolymer reacts with the carboxyl group in the monomer, it will not form a gel. It goes without saying that the selection should be made within a reasonable range.

As such other copolymerizable vinyl monomers, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or hydroxy 7-ethyl vinyl ether can also be used. It goes without saying that the amount of these to be used should be selected within a range that does not result in gelation even if the hydroxyl group and (β-methyl)glycidyl group react, as with the polymeric monomer.

On the other hand, the functional group-containing vinyl copolymer (B) mentioned above includes carboxyl group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, or fumaric acid, 2-(meth)acryloyloxyethyl phosphoric acid group-containing vinyl monomers such as acindophosphate or 2-(meth)acryloyloxyglopyru cindophosphate, and/or dimethylamine ethyl (
Obtained by copolymerizing an amino group-containing monomer such as meth)acrylate or diethylaminoethyl (meth)acrylate with other copolymerizable vinyl monomers or hydroxyl group-containing vinyl monomers listed above. This is a typical example, but P2O,
Of course, those obtained by adding can also be used as the phosphoric acid group-containing vinyl copolymer.

The method for preparing the fatty acid-modified vinyl copolymer (A) and the functional group-containing vinyl copolymer (B) described above is not particularly limited, and various methods such as solution polymerization and bulk polymerization may be used. Although this is possible, for the purposes of the present invention, it is best to use solution polymerization because it is easy to form into a paint and the molecular weight can be easily controlled.

It is appropriate that the copolymers (A) and (B) thus obtained are used in a solid weight ratio of B)/K2 of 1/99 to 80/20.

When this (B)/(A) ratio is smaller than 1/99, the absolute amount of copolymer (B) decreases. Even if the ratio is higher than 80/20, the effect on adhesion and gloss will be extremely small, and the object of the present invention cannot be met.On the other hand, if this ratio is higher than 80/20, the copolymer, (A) Since the absolute amount of the fatty acid decreases, even if a copolymer (A) with a high fatty acid content is used, the air curability and flexibility of the coating film, which are the characteristics of modification with fatty acids, cannot be expected. This would no longer meet the purpose of the present invention.

In the present invention, a resin composition that satisfactorily achieves the object of the present invention can be obtained by simply mixing these copolymers (A) and (B), but the present invention further provides a crosslinking agent (C) component. Resin compositions are also provided which also incorporate amine resins or incyanate prepolymers.

By the way, the copolymer (A) already contains fatty acids and (β
-Methyl)There are hydroxyl groups generated by reaction with glycidyl groups, and when a vinyl monomer containing hydroxyl groups is also used as the copolymer (B), the hydroxyl groups derived from this are sufficient. Since crosslinking and curing are possible, in the present invention, the necessity of the crosslinking agent (component C1) should be determined depending on the required coating film performance, the material of the object to be coated, etc.

Here, representative isocyanate prepolymers include a hexamer of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, or a trimethylolpropane adduct of tolylene diisocyanate. In addition, of course, any of those used in ordinary two-component urethane paints can be used.

The blending amount of such prepolymer is the same as that of the copolymer (
OH/NC0=110.3 to 1/1 in equivalent ratio with respect to the total of each hydroxyl group of A) and copolymer (Bl)
．． 5, preferably within the range of 110.5 to 1/1.2.

On the other hand, typical examples of the amine resin include amino compounds such as melamine, urea, and benzoguanamine.
It is an etherified product obtained by reacting one or more amino resins with formaldehyde or its equivalent substance, and such amino resins may be used alone or in combination.

The amount of the amine resin blended is within the range of 10 to 60% by solid weight based on the total amount of the copolymer (AI and copolymer (B)) from the viewpoint of coating film performance. However, the amount of such amino resin is the copolymer (A),
Since it is determined by considering the amount of hydroxyl groups in (B), the type of the amino resin, the required coating film performance, etc., the present invention is not limited only to the above range.

In addition, as mentioned above, the fatty acid-modified vinyl copolymer can be obtained by synthesizing a (β-methyl)glycidyl group-containing vinyl copolymer by solution polymerization according to a conventional method, and then adding a fatty acid. The temperature of both the polymerization and addition reactions and the catalyst for the addition reaction are not particularly limited. (, On the other hand, in the case of an addition reaction, the temperature should be higher than that during the polymerization reaction to accelerate the reaction.
In this case, a conventional addition reaction catalyst may be used to accelerate the reaction.

As the solvent used for each of the above-mentioned copolymers (N and ff1B), commonly used solvents are used depending on the type of each copolymer. Aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and n-butyl acetate; alcohol solvents such as methanol and n-butanol; or ketones such as methyl ethyl ketone and methyl inbutyl ketone. It is also possible to use aliphatic solvents such as mineral spirits, and the amount of such solvent used also depends on the amount of fatty acid used for the addition reaction and the composition of the (Al, (Bl) covalent mixture. It is not uniform and should be determined by these dependent factors.

The curing conditions for the composition of the present invention are not uniform, as there are various types of curing such as curing at room temperature or hardness by heating, and appropriate curing temperatures. You should choose.

Next, the present invention will be described with reference to Reference Examples, Examples, and Comparative Examples, in which all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 [Fatty acid modified vinyl copolymer (preparation example of AJ)]
In a four-way flask equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer, add xylene i, o o o
D-tert-butyl peroxide (DTBPO)
2// was charged, the temperature was raised to 125°C, and at the same temperature 200 parts of styrene (3t) methyl methacrylate (MMA) 300//n
-Butyl methacrylate (n-BMA) 200〃
n-butyl acrylate) (n-BA) 2
00 Glycidyl methacrylate (GMA)
100 parts azobisisobutyronitrile (AIBN)
10//l-butyl perbenzoate (TB
PB) 4/ was added dropwise over 4 hours, and then 12
After continuing the reaction for an hour and confirming that the non-volatile content (NY) was 509%, 2 [10 parts of soybean oil fatty acid was added and the temperature was raised to 150°C, and the temperature was kept at the same temperature until the acid value was around 2. After the reaction, 200 parts of xylene was added until NY was 50.
A transparent resin solution with a viscosity (Gardner: same hereinafter) of 21, a hydroxyl value of 14.9, a color number of 1, and an acid content of 1.8 was obtained.

Reference Example 2 [Same as above] In a flask similar to Reference Example 1, 979 parts of turpentine and 2
480 parts of St, 200 parts of MMA, 20 parts of n-BA, GM
250 parts of A, 1 betucosol P-'470-7 [
1j 71 parts of [long oil alkyd resin manufactured by Dainippon Ink & Chemicals ■], 10 parts of AIBN, 5 parts of t-butylperoxy-2-ethylhexanate (TBPO), and T
6 parts of BPB was added dropwise over 5 hours, and the reaction was continued at the same temperature for 4 hours after the addition, resulting in an NV of 48.1%.
A glycidyl group-containing vinyl copolymer solution which becomes waxy when cold and is insoluble in turpentine was obtained; 150 parts of dehydrated castor oil fatty acid, 150 parts of soybean oil fatty acid, 100 parts of coconut oil fatty acid and 2-methyl Imidazole (2-M
After adding 04 of IZ) and reacting at 160°C until the acid value reached around 2, 30 parts of Turpen's 4 was added and NY was 50.8.
%, a viscosity of ST, an acid value of 1.5 Te, and a color number of 2. A transparent resin solution was obtained.

Reference Example 6 [Same as above] In a flask similar to Reference Example 1, 600 parts of xylene, 300 parts of n-butyl acetate (n-BuAC), and BT
Charge 2 parts of BPO and raise the temperature to 125°C, and 65% of St.
0 parts, 90 parts of MMA, 170 parts of n-HMA, n-B
100 parts of A, β-hydroxyethyl methacrylate (
160 parts of β-HEMA), 60 parts of β-methylglycidyl methacrylate (MGMA), 10 parts of AIBN,
10 parts of TBPO and 4 parts of TBPB were added dropwise over 5 hours, and the reaction was continued for 8 hours at the same temperature even after the dropwise addition was completed.
After confirming that 490% of soybean oil fatty acid
00 parts and 01 parts of 2-MIZ were added and reacted at the same temperature until the acid value reached around 1.2, and then 100 parts of xylene was added to give an NV of 49.9%, a viscosity of 22, A transparent resin solution having a color number of 2, an acid value of 1.1, and a hydroxyl value of 25.8 was obtained.

Reference Example 4 In a flask similar to Reference Example 1, 1.000 parts of turpentine and 2 parts of DTBPO'4 were charged, the temperature was raised to 125°C, and S
200 copies of t, 200 copies of MMA, 600 copies of GMA,
10 parts of AIBN, 10 parts of TBPO, and 4 parts of TBPB were added dropwise over 6 hours, and the reaction was continued for 10 hours at the same temperature to complete the reaction. The glycidyl group-containing vinyl copolymer solution obtained here is transparent when heated;
There was no solubility at ℃ (it was in a cloudy state).

Next, i, o o o parts of soybean oil fatty acid and 200 parts of linseed oil fatty acid were added to this solution and reacted at 160°C until the acid value reached around 1, and then 466 parts of turpentine was added.

The resin solution obtained here has a NV of 60.7% and a viscosity of 2.
It was transparent with a color number of 2 and an acid value of 0.8.

Reference Example 5 In a flask similar to Reference Example 1, xylene i, ooos
and 2 parts of DTBPO were charged, the temperature was raised to 125°C, and St
400 copies of n-BMA, 211 copies of n-BA, 150 copies of n-BA
100 copies of Acryo=Tori# (AN), 7 copies of GMA
5 parts, β-HEMA 17) 64 parts, 10 parts of AIBN, 3 parts of TBPO, and 4 parts of TBPB were added dropwise over 4 hours, and the reaction was continued for 12 hours at the same temperature, followed by flax seedling. 150 parts of fatty acids and 0.0 parts of boron trifluoride.
Add 1 part and react until the acid value is around 1, then add n-13
150 parts of uAc plus NV of 499% and viscosity of w1
A transparent resin solution with a color number of 6 and an acid value of 09 was obtained.

Reference Example 6 [Preparation example of phosphoric acid group-containing vinyl copolymer EB)] In a flask similar to Reference Example 1, 60 parts of toluene and n-
400 parts of putanol was charged, the temperature was raised to 110°C, and S
200 parts of t, 200 parts of MMA, n-BMA □)
400m, 180 parts of 1l-BA, 20 parts of 2-acryloyloxyethyl '7 side phosphate, AIBN
(7) 10 parts, p-.

6 parts of TBPB and 2 parts of TBPB were added dropwise over 5 hours, and the reaction was continued for 10 hours at the same temperature until the NV was 501.
%, an acid value of 4.1, a viscosity of T-U2, and a color number of 1 or less.

Reference Example 7 [Preparation example of carboxyl group-containing vinyl copolymer EBI] In a flask similar to Reference Example 1, xylene 266
400 parts of n-BuAc and 2 parts of BTBPO were heated to 120°C, and 600 parts of St, n-BM
400 parts of A, 120 parts of β-HEMA, 60 parts of methacrylic acid (MAA), 120 parts of lauryl methacrylate
15 parts of AIBN, 15 parts of TBPO and TBP
4 parts of B were added dropwise over 6 hours and then reacted for 10 hours at the same temperature, resulting in an NV of 61.0%, a viscosity of 2, an acid value of 25.6, a color number of 1 or less, and A transparent resin solution with a hydroxyl value of 60.1 was obtained.

Reference Example 8 [Preparation example of amino group-containing vinyl copolymer mB)]
Except that the same amount of dimethylaminoethyl methacrylate was used instead of MAA, the same procedure as in Reference Example 7 was carried out, with NY being 61.1% and the viscosity being z3. The y value is 0.8, the number of colors is 4,
A transparent resin solution having a hydroxyl value of 608 was obtained.

Examples 1 to 6 and Comparative Examples 1.2 Each fatty acid-modified vinyl copolymer obtained in Reference Examples 1 to 5 (
A) and each functional group-containing vinyl copolymer (Bl) obtained in Reference Examples 6 to 7 were mixed in the proportions shown in Table 1, and titanium oxide was further added so that the PWC was 60%. After kneading in a sand mill for 1 hour, add a dryer.If you want to add crosslinking agent (c)yc, add it here and then adjust the viscosity with thinner to a Ford cup/164 for 20 seconds. As a result, a paint composition was obtained.

At this time, the dryer used was a mixture of cobalt naphthenate having a metal content of 6% and lead naphthenate having a metal content of 24% in a weight ratio of 1:1.

On the other hand, in Example 1.4 and Comparative Example 1, the thinner used was toluene/xylene/methyl in butyl ketone/
Ethyl acetate #/n-BuAc/n-Pucnoru 35/3
Using a mixed solution of 5/1015/1015<M amount ratio),
In Example 2.5 and Comparative Example 2, “Kwazol 1.DD
Ojl: Aromatic solvent (manufactured by Maruzen Sekiyu)/n-butanol/butylcerone lubricant (70/20/10 (weight ratio)); in Examples 6 and 6, toluene/xylene/ethyl acetate/n-BuAc was used. A mixed solution of 20/60/10/20/20 (weight ratio) was used.

Thereafter, each of the resulting paints was separately sprayed onto an iron plate that had been previously coated with a primer, and then, in Example 1.4 and Comparative Example 1, it was allowed to stand for 96 hours before being applied. 6 at 150°C in Example 2.5 and Comparative Example 2.
After drying at 80° C. for 60 minutes in Examples 6 and 6, each film was left to stand for 72 hours, and then the performance of each coating film was examined.

The results are summarized in Table 2.

Claims (1)

[Claims] Copolymerizable with 00 to 60% by weight of styrene, preferably 10 to 5% by weight of ON, and 95 to 6M% by weight of glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate and/or β-methylglycidyl methacrylate, and these monomers. 100 parts by weight of a vinyl copolymer containing a glycidyl group and/or β-methylglycidyl group obtained by copolymerizing 5 to 97 weight % of other monomers with an iodine value of 60 to 200.
A fatty acid-modified vinyl copolymer (A) obtained by adding 5 to 190 parts by weight of a fatty acid, and a vinyl copolymer having at least one functional group selected from the group consisting of a carboxyl group, a phosphoric acid group, and an amine group. Combined (B) is mixed in a solid weight ratio of B)/(A) = 1/99 to 80/20, and if necessary, amino resin or incyanate prepolymer (C) is also blended. A resin composition for paint made of the following.