JPH07138521A - Vinyl copolymer for coating and coating resin composition containing the same - Google Patents

Abstract

PURPOSE:To improve stability to color mixing by copolymerizing a vinyl monomer having a phosphate group with other copolymerizable vinyl monomer in a given proportion to form a copolymer having a specific solubility parameter. CONSTITUTION:A mixture of 0.01-10wt.% vinyl monomer containing a phosphate group, e.g. methacryloyloxyethyl phosphate, 90-99.99wt.% one or more copolymerizable vinyl monomers, e.g. methyl methacrylate and ethyl acrylate, and a xylene solution of a radical-polymerization initiator, e.g. t-butyl peroxyoctoate, is dropped into a solvent, e.g. toluene, heated to a reaction temp. in an inert gas atmosphere. A polymerization initiator is further added at a certain time after completion of the dropping, and the reaction is conducted for a given time. Thus, the copolymer having a solubility parameter of 8.2 or higher and a ratio of weight-average mol.wt. to number-average mol.wt. of 2.0-15.0 is obtained. This copolymer is mixed as a base resin with various paint additives to obtain the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful vinyl copolymer for paints, and a resin composition for paints containing the copolymer as an essential film-forming component.

More specifically, the present invention relates to a vinyl copolymer for a coating having a phosphoric acid group as an essential functional group in the molecule and a resin composition for a coating containing the copolymer as an essential component. In particular, a vinyl copolymer for coating obtained using a phosphoric acid group-containing vinyl monomer as an essential monomer component, and a coating resin composition containing the copolymer as an essential component,

In particular, a vinyl-based resin for paints, which is excellent in color mixing stability with a color-dispersed pigment for solvent-based paint toning, which is marketed under the trademark "Unirant 55" [a product of Unilant Co., Ltd.] The present invention also relates to a polymer and, at the same time, to a resin composition for coating material, which comprises the copolymer as an essential film-forming component.

[0004]

2. Description of the Related Art Up to now, paints using a vinyl copolymer as a binder have used pigments such as titanium oxide, calcium carbonate, clay, rouge, ocher, carbon black, cyanine green and cyanine blue. In many cases, various types of white base paints, colored base paints, and the like are mixed in the case of toning such paints.

The technique itself for improving the pigment dispersibility or color mixing stability in these systems is disclosed in, for example, JP-A-54-62294 and JP-A-5-62294.
It is disclosed in Japanese Patent Publication No. 7-202354 or Japanese Patent Publication No. 56-127671 and the like, and is already well known.

However, in recent years, color fashion has been developed in various fields, and in response to this, the toning of paints has been diversified, and the toning amount of each color has become smaller. It is the actual situation.

Further, due to the reduction of the number of skilled workers and the shortening of the coating process, the simplification of elaborate toning work is urgently desired.

However, the conventional paint using a vinyl-based copolymer as a binder may have a limitation in the toning method depending on the composition of the vinyl-based copolymer. It may take some time.

Therefore, as a coloring base for toning,
"UNILANT 55", which is a coloring dispersion pigment for solvent-based paint toning containing a surfactant and / or a polar solvent, and if necessary, a pigment dispersant as a main component, is extremely responsive to the above-mentioned needs. Since it can be matched with, it is increasingly used in paint color matching.

Even in this case, a white base coating using a conventional vinyl-based copolymer as a binder, for example, a polar group such as an amino group is used as in the above-mentioned publications. In the case of a paint in which a white base paint using a copolymer having a basicity as a binder and a coloring disperse pigment "UNILANT 55" are mixed and toned by a technique of improving pigment dispersibility, After all, the major drawback is that the color mixing stability is poor, and that color separation and color difference when overcoated are observed.

[0011]

However, in view of the existence of various drawbacks in the prior art as described above, the present inventors, in particular, call it "Unirant 55".
Research has been earnestly started in search of a paint resin and a paint resin composition having excellent practicability, which are excellent in mixing stability with a color dispersion pigment for solvent-based paint toning.

[0012] Therefore, the problem to be solved by the present invention depends on one and, in addition to the pigment dispersibility, which is one of the drawbacks of conventional resins or resin compositions, the above-mentioned color dispersion pigment "Unirant". It is an object of the present invention to provide an extremely highly practical vinyl-based copolymer for paints, which is also excellent in color mixing stability with "55", and a resin composition for paints containing the copolymer as an essential film-forming component.

[0013]

Therefore, the present inventors have
As a result of intensive and intensive studies, focusing on the problems to be solved by the invention as described above, as a result, a radical polymerization initiator was obtained by using vinyl monomers having a phosphate group-containing vinyl monomer as an essential monomer component. A specific vinyl which is obtained by copolymerization in the presence of a vinyl copolymer and has a solubility parameter (hereinafter abbreviated as SP value) of 8.2 or more in the vinyl copolymer obtained. When using a system copolymer,

Further, the SP value is 8.2 or more, and
In the case where a specific vinyl-based copolymer having an Mw / Mn ratio of 2.0 to 15.0 is used, in particular, when a color-dispersed pigment for color-adjusting a paint of "UNILANT 55" is used as a color base. The present invention has been completed here by discovering that the color mixing stability can be dramatically and dramatically improved.

That is, the present invention basically requires a vinyl copolymer for paints having at least one phosphoric acid group in a molecule as a specific functional group, and in particular, a phosphoric acid group-containing vinyl monomer. The present invention also provides a vinyl-based copolymer for a coating, which uses the above-mentioned monomer component as a monomer component, and also provides a resin composition for a coating containing the copolymer as an essential base resin component. ,

Specifically, 0.01 to 10% by weight of the phosphoric acid group-containing vinyl monomer (a) and the vinyl monomer are used.
Other vinyl monomers copolymerizable with (a)
A vinyl copolymer obtained by copolymerizing 90 to 99.99% by weight of (b) with 100% by weight of the total amount of monomers in the presence of a radical polymerization initiator. So, the SP of the vinyl copolymer
First of all, it is intended to provide a vinyl-based copolymer for a paint having a value of 8.2 or more,

Further, each has an SP value of 8.2 or more and a weight average molecular weight (Mw) / number average molecular weight (M
It is also an object of the present invention to provide an extremely highly practical resin composition for coatings, which uses a vinyl-based copolymer having n of 2.0 to 15.0 as an essential base resin component. .

Here, of the various constituents of the above-mentioned vinyl copolymer for paints, only the particularly representative ones as the essential components of the phosphoric acid group-containing vinyl-based monomer (a) are shown. If

Dialkyl [(meth) acryloyloxyalkyl] phosphates; (meth) acryloyloxyalkyl acid phosphates; dialkyl [(meth)
Acryloyloxyalkyl] phosphite; or (meth) acryloyloxyalkyl acid phosphite,

Alkylene oxide adducts of the above acid phosphites; or various epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate or methylglycidyl (meth) acrylate, and phosphoric acid or phosphorous acid or their acid esters. Ester compounds and the like.

The amount of the phosphoric acid group-containing vinyl monomer (a) used is 0.01 based on the total amount of the monomers.
The range of 10% to 10% is preferable, and the range of 0.05% to 5% is suitable.

When the content is less than 0.01%, the color mixing stability in the case of using the color dispersion pigment "UNILANT 55" for toning, that is, color separation, color difference upon repeated coating, etc. You can't expect the effect above,

On the other hand, when it is used in excess of 10%, the viscosity of the resin becomes too high.
In any case, it becomes turbid, and further, depending on the type of pigment, the storage stability is lowered, which is not preferable.

Next, as the other vinyl-based monomer (b) copolymerizable with the above-mentioned phosphoric acid group-containing vinyl-based monomer (a) component, a coloring dispersion pigment "UNILANT 5" is used.
The component as the binder of 5 ”has a surfactant and / or a polar solvent and, if necessary, a pigment dispersant as a main component, and thus has a very high polarity, and thus, such a vinyl-based monomer is used. The component (b) also needs to have high polarity.

That is, when the copolymer of the above-mentioned component (a) and this component (b) is converted into the SP value,
It is necessary to select appropriately so that it will be 8.2 or more,
That's what it means.

If the SP value is less than 8.2, the compatibility with "UNILANT 55" tends to deteriorate, and the color mixing property when "UNILANT 55" is used for color matching is inevitable. However, it is not preferable because it will decrease.

Here, a method of calculating the SP value will also be mentioned. At that time, the SP value of the copolymer is based on the assumption that the SP value of each monomer satisfies the additivity on a weight basis.

The SP value of each monomer is shown in "Journal of the" written by KL Hoy.
Paint Technology (Journal Of Pai
nt Technology) "Volume 42, 541
No., page 76 (1970)

For example, styrene = 9.3.
5; Methyl methacrylate = 9.23; Ethyl acrylate = 8.81; Butyl acrylate = 8.25; Isobutyl methacrylate = 8.15; 2-Ethylhexyl acrylate = 7.87; 2-Hydroxyethyl acrylate = 9.90 ; Or vinyl acetate = 9.05, etc., and for a monomer for which there is no literature value, the calculated value by the Hoy method is adopted.

Therefore, the above-mentioned component (b),
As the vinyl-based monomer copolymerizable with the monomer component (a), as long as the SP value of the copolymer does not deviate from the object of the present invention or does not impair the effects of the present invention, Various co-monomers (comonomer) can be adopted.

Further, as long as it does not deviate from the object of the present invention or does not impair the effects of the present invention, the obtained copolymer is not necessarily a solvent-soluble type, and is so-called NAD (non-aqueous). Dispersion)
May be.

In other words, the following various compounds can be mentioned, only by exemplifying the particularly representative one as the copolymerizable vinyl monomer which is the component (b).

(A): Styrene, α-methylstyrene,
various aromatic vinyl monomers such as p-tert-butylstyrene or vinyltoluene;

(B): Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n
-Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate

Or benzyl (meth) acrylate, isobornyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, 4-tert-butyl (meth) acrylate or alkoxyalkyl (meth) acrylate, Various (meth) acrylates;

(C): Various vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate or "Veova" (vinyl ester manufactured by Shell Co., Netherlands);

(D): Various unsaturated dicarboxylic acids represented by maleic acid, fumaric acid or itaconic acid, such as dimethyl maleate, diethyl maleate, diethyl fumarate, dibutyl fumarate or dibutyl taconate. Diesters of acids and monohydric alcohols;

(E): Acrylonitrile, vinyl chloride,
Vinyl-based monomers having no so-called functional group (reactive polar group) represented by various (halogen) olefins such as vinylidene chloride, vinyl fluoride or vinylidene fluoride;

(F): such as (meth) acrylamide, dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide or alkoxylated N-methylolated (meth) acrylamide, Various amide bond-containing vinyl monomers;

(G): Various unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid or citraconic acid as a carboxy group-containing vinyl monomer, and ethanol or n. Various α, β-ethylenically unsaturated carboxylic acids, such as monoesters with various monohydric alcohols, such as butanol;

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

Alternatively, various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters such as polyethylene glycol-mono (meth) acrylate and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid,
Methyl hexahydrophthalic acid, tetrahydrophthalic acid,
Benzenetricarboxylic acid, benzenetetracarboxylic acid,
"Hymic acid" [a product of Hitachi Chemical Co., Ltd .; "Hymic acid" is a registered trademark of the same company. ], Adducts of various polycarboxylic acids with anhydrides, such as tetrafluorophthalic acid or dodecyl succinic acid;

(H): Glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate or (meth) allyl glycidyl ether, α,
β-ethylenically unsaturated carboxylic acids or mono-2-
(Meth) acryloyloxy monoethyl phthalate, various hydroxyl-containing vinyl monomers, and various unsaturated carboxylic acids such as an equimolar addition of the polycarboxylic acid,

"Epiclon 200, 400, 441,
850 or 1050 "[epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.] or" Epicoat 82 "
Various types of polyepoxy compounds having at least two epoxy groups in one molecule, such as "8, 1001 or 1004" (epoxy resin manufactured by Shell Co., Netherlands),
Various epoxy group-containing vinyl monomers obtained by addition reaction at an equimolar ratio;

(I): 2-hydroxyethyl (meth) acrylate as a hydroxyl group-containing vinyl monomer, 2
-Hydroxypropyl methacrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-2- Hydroxyethyl-monobutyl fumarate

Alternatively, polypropylene glycol or polyethylene glycol mono (meth) acrylate, or "Plaxel FM or FA monomer" [caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.]
And various hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as
These are adducts of these α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters with ε-caprolactone.

Among the above-mentioned copolymerizable vinyl-based monomers (b), carboxyl group-containing vinyl-based monomers (G), epoxy group-containing vinyl-based monomers (H), hydroxyl group-containing vinyl-based monomers (R), etc. The vinyl copolymer is used in cases where it is desired to impart a crosslinking function or an internal catalyst function, or to improve the adhesiveness to the material, and the amount used depends on each purpose. Therefore, it may be used in an appropriate dose.

Further, (nu): such as perfluorocyclohexyl (meth) acrylate or N-iso-propyl perfluorooctanesulfonamidoethyl (meth) acrylate,
Containing various (per) fluoroalkyl groups,
-Vinyl esters, -Vinyl ethers,-(meth)
Various fluorinated polymerizable compounds such as acrylates or -unsaturated polycarboxylic acid esters;

(L): Vinylethoxysilane, α-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth) acrylate or "KR-21.
5 or X-22-5002 "[Shin-Etsu Chemical Co., Ltd.
Various products, such as various silicon-based monomers.

Further, for the purpose of further improving the weather resistance, for example, (wo): [NORBLOC 7966] [NORAMCO (NORAMCO) as disclosed in US Pat. No. 4,528,311]. Company's product] such as benzotriazole-based acrylic monomers; or “ADEKA STAB T-37 or LA-82” [Asahi Denka Co., Ltd.
Various polymerizable UV absorbers or polymerizable stabilizers, such as

(W): "AA-6, AS-6, AN-6 or AB as disclosed in JP-A-63-128002 or JP-A-1-13261.
-6 "[all are products of Toagosei Kagaku Kogyo Co., Ltd.], and various high-molecular-weight monomers (macromonomers or macromers) having a functional group end capable of copolymerization can be mentioned.

Furthermore, when the main purpose is to further improve the pigment dispersibility of the obtained copolymer, or to improve the solubility and the non-volatile content during coating, ,

(F) Unsaturated bond-containing resins are suitable, and specifically, polyester resin type (including oil-modified type) or vinyl type copolymer or acrylic type copolymer is preferable. It is also possible to modify by means of these.

Japanese Examined Patent Publication No. 45-22011 and No. 46-
20502, 44-7134, and JP-A-4
As disclosed in JP-A-8-78233 or JP-A-50-58123, a raw material component having a copolymerizable unsaturated bond is essential, and by reacting with other raw material components, in the resin skeleton, It is in the form of having a copolymerizable unsaturated bond,

Alternatively, as disclosed in JP-B-49-47916 and JP-A-50-6223, first, a saturated polyester having no copolymerizable unsaturated bond is first obtained, and then the saturated polyester is obtained. Examples thereof include a compound having a functional group such as a hydroxyl group and a carboxyl group present therein, and a functional group having reactivity with a diepoxy compound and a vinyl group.

In the case of carrying out such various modifications, it is particularly recommended that the modification amount be within a range of about 0.1 to 10.0% by weight.

It is said that various monomers as the component (b) should be appropriately selected so that the SP value of the copolymer with the above-mentioned monomer components (a) becomes 8.2 or more. In addition to the above, copolymerizability, coating workability, gloss, hardness, burnability, weather resistance, drying property, solvent resistance, compatibility, dilutability, solubility, price and stain resistance, etc. From the viewpoint, the amount of each monomer component and the combination thereof should be appropriately determined within the range of 90 to 99.99% by weight.

The vinyl copolymer for coating material according to the present invention is
Using the respective raw material components (a) and (b) described above, various known and conventional methods such as a batch-type, semi-batch type or continuous-type solution polymerization method under normal pressure or under pressure are used. It can be prepared by making full use of a polymerization method.

At that time, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t
ert-butyl peroxybenzoate (TBPB),
tert-butyl peroxyoctoate (TBP
O), tert-butyl hydroperoxide, di-te
rt-Butyl peroxide (DTBPO)

Or cumene hydroperoxide (CH
P) such as various known and conventional radical-generating polymerization catalysts (radical polymerization initiators) are appropriately selected and used according to the polymerization conditions, or a mixture of several types is used. Of course, it can be done.

Further, as the solvent to be used at that time, any of known and commonly used solvents can be used. Of these, only typical ones are exemplified by toluene and xylene. Various aromatic hydrocarbons; various esters such as ethyl acetate, butyl acetate, cellosolve acetate;

Or acetone, methyl ethiketone,
Various ketones such as methyl isobutyl ketone; various alcohols such as n-butanol and isobutanol; and various ethers (ether alcohols) such as butyl cellosolve.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), that is, the Mw / Mn ratio, of the thus obtained vinyl copolymer for coating composition of the present invention is as follows.
A large range of about 2.0 to 15.0 is suitable, and a range of about 3 to 9 is preferable.

When the Mw / Mn ratio, that is, the molecular weight dispersion ratio is less than 2.0, the pigment dispersibility, color mixing stability, drying property, water resistance and the like tend to be deteriorated. On the other hand, if it exceeds 15.0 and becomes too large, inconvenience is likely to occur in storage stability, coating workability, dilutability, and coating non-volatile content.

When the copolymer of the present invention itself has a so-called functional group such as a hydroxyl group, a carboxyl group and / or an epoxy group, a compound having reactivity with these functional groups,

For example, a polyisocyanate compound,
Amino resin, a polycarboxylic acid compound, a polyepoxy compound, a chelate compound, or the like, a commonly known compound as a so-called crosslinking agent component, is compounded as a curing agent,
Of course, it can also be used as a curable paint,

Further, various additives for coatings, which are usually known and used in the art, such as pigment dispersants, leveling agents, ultraviolet absorbers, light stabilizers or curing accelerators. Needless to say, it is possible to use the usual kind,

If it is compatible with the copolymer of the present invention and becomes soluble, the purpose is to improve various performances.
Unless deviating from the object of the present invention, and within a range not impairing the effects of the present invention,

Plasticizers, nitrification cotton or cellulose derivatives such as cellulose acetate butyrate (CAB); or acrylic copolymer resins, acrylated alkyd resins, alkyd resins, silicone resins, fluororesins or epoxy resins, It is also possible to appropriately use other various resins in combination.

Thus, the coating resin composition of the present invention, that is, the phosphoric acid group-containing vinyl copolymer for coating as described above, is a monomer in which a phosphoric acid group-containing vinyl monomer is essential. It is possible to obtain a highly practical resin composition for coating, which comprises a vinyl copolymer for coating obtained by using the mixture as an essential base resin component.

The thus-obtained phosphoric acid group-containing vinyl copolymers for paints and the resin compositions for paints containing the copolymers as essential base resin components are both widely used and widely used as ferrous and non-ferrous general-purpose products. It can be used for coating metal materials or products, particularly for coating roofs or roof tiles including interior and exterior of buildings.

[0072]

EXAMPLES Next, the present invention will be explained more concretely by reference examples, examples and comparative examples. In addition,
In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 (Preparation Example of Copolymerizable Unsaturated Bond-Containing Resin) In a four-necked flask equipped with a stirrer, a thermometer, a reaction product water remover, and a nitrogen gas introduction tube, 51 parts of isophthalic acid were added.
3 parts, 19 parts of maleic anhydride, 106 of adipic acid
, 391 parts of neopentyl glycol, 83 parts of trimethylolpropane, 30 parts of pentaerythritol and 0.005 parts of an antifoaming agent were charged and the temperature was raised to 180 ° C.

After being kept at the same temperature for 2 hours,
The temperature was raised to 220 ° C. over 3 hours and kept at the same temperature in a nitrogen gas atmosphere until the acid value was 9 or less, and then the non-volatile content was adjusted to about 60% with acetic acid n. -Diluted with butyl to obtain a solution of the objective resin having a nonvolatile content of 60%, a Gardner viscosity (hereinafter abbreviated as viscosity) of U at 25 ° C, and an acid value of 5.0. It was

Reference Example 2 (Same as above) 382 parts of dehydrated castor oil fatty acid, 5 of maleic anhydride
Parts, 34 parts of phthalic anhydride, 100 parts of neopentyl glycol and 0.005 parts of antifoaming agent were added, and in addition, xylene was used as a solvent. In the same manner as in Example 1, a solution of a dehydrated castor oil-modified target resin having a nonvolatile content of 60%, a viscosity of U, an acid value of 3.6, and an oil length of 40% was obtained.

Example 1 400 parts of toluene, 8 parts of the resin solution obtained in Reference Example 1, 350 parts of vinyl acetate were placed in a four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet and a condenser.
, 5 parts of BPO and 5 parts of AIBN,
The temperature was raised to 5 ° C.

After keeping at the same temperature for 3 hours, 200 parts of vinyl acetate, 3 parts of acrylic acid, 440 parts of methyl methacrylate and 2 parts of methacryloyloxyethyl phosphate, and 100 parts of toluene were added. , 5 parts of TBPO and 4 parts of AIBN were added dropwise over 4 hours.

Two hours after the completion of this dropping, TBPO 2 was added.
After adding another part and continuing the reaction as it was, the desired nonvolatile content was reached in about 18 hours.
Part added, with a nonvolatile content of 50%, a viscosity of Z ₂ -Z ₃
, The acid value is 1.8, the SP value is 9.16, and the Mw
A solution of a vinyl-based copolymer for paint having a / Mn ratio of 6.5 was obtained.

Example 2 In the same manner as in Example 1 except that the resin solution obtained in Reference Example 2 was used instead of the resin solution obtained in Reference Example 1 as the initial charge. Nonvolatile content is 50%
The viscosity is Z, the acid value is 2.5, and the SP value is 9.14.
Then, a solution of a vinyl-based copolymer for coating having a Mw / Mn ratio of 6.3 was obtained.

Example 3 400 parts of toluene, 350 parts of vinyl acetate, 5 parts of BPO and 5 parts of AIBN were placed in a four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet and a condenser.
A part was charged and the temperature was raised to 85 ° C.

After keeping the same temperature for 3 hours, 156 parts of vinyl acetate, 50 parts of n-butyl acrylate, 442 parts of methyl methacrylate and 2 parts of methacryloyloxyethyl phosphate and toluene were added. 100 parts, 5 parts of TBPO and 4 parts of AIBN
The mixture consisting of 1 part and 4 parts was added dropwise over 4 hours.

Two hours after the completion of this dropping, TBPO 2 was added.
After adding another part and continuing the reaction as it was, the desired nonvolatile content was reached in about 18 hours.
Parts, the nonvolatile content is 50% and the viscosity is Z ₁ -Z _2.
, The acid value is 0.3, the SP value is 9.11.
A solution of a vinyl-based copolymer for paint having a / Mn ratio of 3.5 was obtained.

Example 4 A four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet and a condenser was charged with 500 parts of toluene and heated to 110 ° C. to obtain 500 parts of methyl metaacrylate. , A mixture of 480 parts of ethyl acrylate and 20 parts of methacryloyloxyethyl phosphate, 230 parts of xylene and 4 parts of TBPO,
It was added dropwise over 4 hours.

Two hours after the completion of the dropping, TBPO 2 was added.
After adding another part and continuing the reaction as it was, the desired nonvolatile content was reached in about 18 hours.
Parts, the nonvolatile content is 50% and the viscosity is Z ₄ -Z ₅
, The acid value is 0.2, the SP is 9.08, and the Mw
A solution of a vinyl-based copolymer for paint having a / Mn ratio of 3.8 was obtained.

Example 5 200 parts of styrene, 470 parts of methyl methacrylate, 100 parts of ethyl acrylate, 129.5 parts of 2-ethylhexyl acrylate, 100 parts of β-hydroxyethyl methacrylate and 100 parts of methacryloyloxy were added dropwise. Nonvolatile content was 50% and the viscosity was Z in the same manner as in Example 3 except that a mixture of 0.5 parts of ethyl phosphate, 230 parts of xylene and 4 parts of TBPO was used. _3- Z ₄ with an acid value of 0.2
And the SP value is 9.10 and the Mw / Mn ratio is 2.8.
A solution of a vinyl copolymer for paint was obtained.

Example 6 200 parts of styrene, 470 parts of methyl methacrylate, 100 parts of ethyl acrylate, 220 parts of 2-ethylhexyl acrylate and 10 parts of methacryloyloxyethyl phosphate, and 230 parts of xylene were added dropwise. , 4 parts of TBPO, except that the non-volatile content was 50%, the viscosity was ZZ ₁ , and the acid value was 0.2, in the same manner as in Example 3.
And the SP value is 8.94 and the Mw / Mn ratio is 3.3.
A solution of a vinyl copolymer for paint was obtained.

COMPARATIVE EXAMPLE 1 A mixture of 200 parts of styrene, 470 parts of methyl methacrylate, 100 parts of ethyl acrylate and 230 parts of 2-ethylhexyl acrylate, 230 parts of xylene and 4 parts of TBPO was added dropwise. In the same manner as in Example 4, except that the nonvolatile content was 50%, the viscosity was Z, the acid value was 0.2, and the SP
As a control, a solution of a vinyl-based copolymer for coating having a value of 8.90 and an Mw / Mn ratio of 4.0 was obtained.

Comparative Example 2 As drops, 156 parts of vinyl acetate, 50 parts of n-butyl acrylate, 442 parts of methyl methacrylate and 2 parts of dimethylaminoethyl methacrylate, 100 parts of toluene, and 5 parts of TBPO were added. And modified to use a mixture consisting of 4 parts of AIBN,
As in Example 3, the nonvolatile content was 50% and the viscosity was Z ₁
And the acid value is 0. 2 and the SP value is 9.11.
As a control, a solution of a vinyl-based copolymer for paint having a / Mn ratio of 3.6 was obtained.

Examples 7 to 12 and Comparative Examples 6 and 7 120 parts of each of the vinyl copolymer solutions for paints obtained in Examples 1 to 6 and Comparative Examples 1 and 2,
40 parts of "Taipeque R-930" [titanium oxide manufactured by Ishihara Sangyo Co., Ltd.] was dispersed by a sand mill to prepare various white enamel having a PWC (pigment weight concentration) of 40%.

Next, with respect to 100 parts of each white enamel, each color of "Unirant 55", that is, Tallow Red as a red color, Red Oxide as a red rust color, and Ocher color (ocher color) As for, yellow oxide,

As a special yellow color, permakal yellow is used.
Navy blue is Tallow Blue, and black is Lamp Black, and each is mixed at a ratio of 3 parts to obtain a mixed color base.

Further, for each 100 parts of white enamel, three colors of red oxide, yellow oxide and lamp black, which are three colors for convenience, were mixed one by one to obtain a mixed color base.

After that, various kinds of mixed color bases thus obtained were diluted with a lacquer thinner,
18-20 with "Foreword Cup No. 4"
Adjust the viscosity so that the viscosity is second, and first check the storage stability of this diluted solution as a performance evaluation test item.
Was visually inspected.

Further, as a performance evaluation test item, a tin plate was spray coated, dried and then flow coated to examine the color difference and gloss.

The results of the various performance evaluation tests obtained as described above are summarized in Table 1.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

<Evaluation method> Regarding the storage stability, the presence or absence of a change in the state after each of the above diluted solutions was stored for one day and night, and the degree of the change were visually determined.

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The color difference is "COLOR MEASURIN
The measurement was performed using "G SYSTEM Sigma-80" [model name manufactured by Nippon Denshoku Industries Co., Ltd.].

Area where color value is less than 0.2 ............ No color difference, almost no area Area where color value is 0.2 to 0.5 ...... Slight color difference exists Color value 0.5 to 2.5 Area where there is a significant color difference Area with a color value exceeding 2.5 There is a significant color difference

The gloss was evaluated by a 60 ° specular reflectance (%) by a conventional method.

[0109]

INDUSTRIAL APPLICABILITY As described in detail above, both the vinyl copolymer for paints of the present invention and the resin composition for paints containing the copolymer as an essential base resin component are, in particular, “UNILANT 55”. It is said that it is excellent in color mixing stability with a colored dispersion pigment for solvent-based paint toning, and has excellent color mixing suitability for such a colored dispersion pigment for solvent-based paint toning.

Therefore, it can be said that the vinyl copolymer for paints of the present invention and the resin composition for paints containing the copolymer as an essential base resin component are both highly practical. .

Claims (8)

[Claims] 1. A vinyl-based copolymer for coatings, which has a phosphoric acid group in its molecule and has a solubility parameter of 8.2 or more. 2. A vinyl copolymer for paints, which comprises a phosphate group-containing vinyl monomer as an essential monomer component and has a solubility parameter of 8.2 or more in the obtained copolymer. 3. The vinyl-based copolymer described above is 0.01 to 10% by weight of the phosphoric acid group-containing vinyl-based monomer (a),
In the presence of a radical polymerization initiator, the above vinyl-based monomer (a) and other vinyl-based monomer (b) that is copolymerizable with 90 to 99.99% by weight are adjusted to 100% by weight as a whole. The vinyl-based copolymer for a coating composition according to claim 2, which is a vinyl-based copolymer obtained by copolymerization with the above-mentioned, and the solubility parameter of the vinyl-based copolymer is 8.2 or more. Copolymer. 4. The vinyl-based copolymer is 2.0 to
It has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio within the range of 15.0.
A vinyl-based copolymer for paint according to any one of 1. 5. A coating material comprising a vinyl copolymer for coating material having a phosphoric acid group in the molecule and having a solubility parameter of 8.2 or more as an essential base resin component. Resin composition. 6. A vinyl copolymer for coatings, which comprises a phosphoric acid group-containing vinyl monomer as an essential monomer component and has a solubility parameter of 8.2 or more as the essential base resin component. A resin composition for coating material, which comprises: 7. The above vinyl-based copolymer comprises 0.01 to 10% by weight of the phosphoric acid group-containing vinyl-based monomer (a),
In the presence of a radical polymerization initiator, the above vinyl-based monomer (a) and other vinyl-based monomer (b) that is copolymerizable with 90 to 99.99% by weight are adjusted to 100% by weight as a whole. 7. The resin composition for coating composition according to claim 6, which is a vinyl-based copolymer obtained by copolymerization with a vinyl copolymer and has a solubility parameter of 8.2 or more. Stuff. 8. The vinyl-based copolymer is 2.0 to
It has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio within the range of 15.0.
The resin composition for paint according to any one of 1.