JP2003252937A - Graft-reaction product and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester or poly (ester-urethane) graft-reaction product that exhibits properties of graft chains without degrading mechanical properties of a base resin. <P>SOLUTION: This graft-reaction product has a polyester main chain, and a polymer from radical-polymerizable monomers as a side chain, the polymer from radical-polymerizable monomers satisfying requirement (1): the weight sum of an electron-accepting monomer having an e value of ≥0.9 and an electron donating monomer having an e value of ≤-0.6 is at least 50 wt.% of the total radical-polymerizable monomers in the polymer, and requirement (2): an aromatic, radical-polymerizable monomer is at least 10 wt.% of the total radical-polymerizable monomers in the polymer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vehicle such as a paint, an ink, a coating agent, an adhesive, or a fiber,
The present invention relates to a graft-modified polyester resin and a graft-modified polyester polyurethane resin which are useful as a processing agent for films and paper products and have excellent mechanical properties. Further, as a form of use thereof, both a solvent-soluble type and a water-dispersed type can be used.

[0002]

2. Description of the Related Art Many techniques for obtaining a graft or block reaction product by polymerizing a radically polymerizable monomer with a polyester resin and a polyurethane resin have been disclosed, and the purpose thereof is, for example, impact resistance as a molding material. It is being studied for various functions such as a compatibilizer aiming at improvement, improvement of adhesion to a base material in application of paints and adhesives, addition of curing characteristics, and improvement of pigment dispersibility.

The solvent-soluble graft modification and water dispersion of low molecular weight copolyesters have been known for a long time, for example, US Pat. No. 3,634,351 and JP-B-57-5.
7065, U.S. Pat.No. 4,517,322, etc., but the polyesters as the subject of them belong to alkyd resins or unsaturated polyester resins, and their molecular weight is very low, and the resulting cured coating film has low bending workability and water resistance. It has the disadvantage of being inferior in sex. As an example of modification in which a polymerizable unsaturated double bond is introduced into the main chain or terminal of a high molecular weight copolyester and a radical polymerizable monomer is grafted or block polymerized thereto, JP-A-57-388
No. 10, JP-A-3-294322, and JP-A No. 5-262870. Examples of the water dispersion means include JP-B-61-578.
74, JP-A-59-223374, JP-A-61-200109, and JP-A-62-525510.

Examples of similar graft or block modifications to polyurethane resins include JP-B-48-19559,
Japanese Patent Publication No. 1-36842, Japanese Patent Application Laid-Open No. 2-102214, Japanese Patent Application Laid-Open No. 5-230166
There are issues, etc. Further, as an example of introducing a hydrophilic functional group into a graft or block chain to disperse it in water, JP-A-46-7
No. 705, JP-A-54-36394, JP-A-54-39488, special table flat
There are 5-501124 (WO91 / 15528), JP-A-5-186543 and the like. All of these are based on a graft polymerization method in an organic solvent. In addition to this, as a special case in the case of leading to water dispersion, a hydrophilic functional group is also introduced into the urethane main chain, and several methods of aqueous emulsion polymerization are proposed, such as Japanese Patent Publication No. 60-42809. ing.

However, in the case of graft modification to a high molecular weight copolyester or polyurethane resin,
Generally, the larger the molecular weight, the easier the crosslinking between resin molecules occurs, so that the graft reaction product tends to gel, but there is a problem.
In these prior arts, only a wide range of monomers are listed for the radical-polymerizable monomer composition used in carrying out the graft reaction, and how to avoid gelation and ensure high graft efficiency. There is no description about the composition, and further, there is no description about how to design the side chain composition in order to bring the mechanical properties of the graft reaction product closer to that of the main chain polymer.

[0006]

That is, the present inventors have found out that the following problems have not been solved in many of these prior arts. When a radical-polymerizable monomer is graft-reacted on a side chain of a polymer chain containing a radical-polymerizable unsaturated double bond in the main chain, 1) gelation often occurs. When gelation avoidance conditions are selected, a binding reaction does not occur between the main chain component and the side chain component, and the reaction product becomes a blend of the main chain component and the side chain component, and the modification purpose is not achieved. 2) The monomer composition ratio of the side chain component actually obtained does not match that at the time of charging, and the sufficient modification purpose is not achieved. 3) Furthermore, as a problem that is extremely important in practical use and has not been clarified at all in the prior art documents, the mechanical properties of the coating film of the graft-modified product are larger than those of the main chain polymer that is not graft-modified. descend. I found that there is a problem.

[0007]

The inventors of the present invention solve the above-mentioned three problems by solving the problems described above, 1),
For 2), considering the electronic state of the polymerizable unsaturated double bond introduced into the main chain, a combination of an electron-accepting monomer and an electron-donating monomer is used as a side chain component. In pursuit of 3), the aromatic dicarboxylic acid component constituting the main chain is introduced with an aromatic unsaturated monomer in the side chain to improve the compatibility by the aromatic ring interaction. The inventors have earnestly sought means for making it possible, and have found that the mechanical properties can be greatly improved, and have reached the present invention.

That is, in the present invention, the main chain contains 60 mol% or more of aromatic dicarboxylic acid in all carboxylic acid components, and
A polyester containing an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol having 6 to 12 carbon atoms and / or an ether bond-containing glycol as a component, or a polyester polyurethane comprising the same And a side chain is a polymer of a radical-polymerizable monomer satisfying the following requirements (1) and (2). (1) An electron-accepting monomer having an e-value of 0.9 or more and an electron-donating electron having an e-value of -0.6 or less in a Q-e value in a polymer of a radically polymerizable monomer that constitutes a side chain. The total weight of the polymerizable monomer accounts for at least 50% by weight of the total radical-polymerizable monomer. (2) In the polymer of the radical-polymerizable monomer forming the side chain, the aromatic radical-polymerizable monomer accounts for at least 10% by weight of the total radical-polymerizable monomer. Is.
In the present invention, a base resin and an electron-accepting or electron-donating radical-polymerizable monomer having a small difference from the e value of the polymerizable double bond of the base resin are allowed to coexist in the reaction solvent in advance. Of the polymerizable double bond of the base resin
A method for producing a graft reaction product, which comprises adding an electron-donating or electron-accepting radical-polymerizable monomer having a large difference from the value and an initiator to each other while heating and stirring and reacting them.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the composition of the radical-polymerizable monomer used in the side chain is such that the e-value of the Q-e value proposed by Alfrey-Price is 0.9 or more, preferably 1.0 or more, more preferably Is mainly composed of a radically polymerizable monomer having a value of 1.5 or more and a monomer having an e value of -0.6 or less, preferably -0.7 or less, more preferably -0.8 or less. To be done.

When the e value is negatively large, it indicates that the compound has a strong electron-donating substituent, and there is an excess of electrons that are not involved in the bond existing in the unsaturated bond portion, so that the double bond and the product thereof are formed. The radicals that represent the charges are negatively biased. On the other hand, if the value is positively large, it means that the compound has a strong electron-withdrawing substituent, and the number of electrons not involved in the bond is insufficient. Represents When copolymerizing a radical polymerizable monomer, a radical polymerizable monomer having an electron donating substituent, that is, a monomer having a large negative e value and a radical polymerizable monomer having an electron withdrawing substituent When a monomer, that is, a monomer having an electronic state opposite to that of a positively large e value is combined, any radicals generated during the polymerization are easily added. Is a monomer in which the positive and negative of the e value are opposite, and when the difference between the e values is large, the tendency becomes remarkable.
As described above, the monomers with greatly different e values are
By taking advantage of the fact that copolymerization actually occurs, it becomes easier for random copolymerization to occur rather than block-like copolymerization. It is possible to get closer.

The unsaturated bond in the resin to be modified is
It is derived from unsaturated dicarboxylic acids such as fumaric acid and itaconic acid, and allyl compounds having a hydroxyl group or a carboxyl group such as glycerin monoallyl ether. Regarding the e value of these compounds, fumaric acid and itaconic acid Since the unsaturated bond has an electron-withdrawing carboxyl group as a substituent,
(1.0 to 2.0 in the case of diester), which is extremely large, and the unsaturated bond has a positively biased charge, resulting in allylation.
In the case of compound, it is extremely large at -1.0 to -2.0 due to allyl resonance, and the unsaturated bond is biased to negative. In the case of grafting, a radical-polymerizable monomer having a high copolymerizability with respect to the unsaturated bond in the resin to be modified (that is, the positive and negative signs are opposite in e value and the difference in e value is large). By using, it is possible to suppress the polymerization alone without reacting with the resin to be modified. That is, the modified resin obtained by copolymerizing fumaric acid having a positively large e value has a large negative value among the combinations of monomers having an e value of 0.9 or more and -0.6 or less, which are essential to the present invention. Grafting efficiency is improved due to easy copolymerization with the monomer, and the modified resin having an allyl group with a negatively large e value is easily copolymerized with a positively large monomer. Also, the grafting efficiency is improved, and in any case, the amount of the homopolymer of the radical-polymerizable monomer that has not reacted with the modified resin can be reduced. Further, the feature of the present invention is that gelation can be suppressed by the ratio of the combination of the monomer having an e value of 0.9 or more and the monomer of -0.6 or less. Conventionally, in the modification of a resin containing an unsaturated bond with a radical-polymerizable monomer, when the amount of unsaturated bond in the resin to be modified is small, sufficient grafting is not performed, and the radical-polymerizable monomer alone is used. If a polymer is produced and the amount of unsaturated bonds is large,
The range of the amount of unsaturated bonds actually usable in the modified resin was extremely narrow because gelation occurred due to the coupling between the graft side chains, but in the present invention, the e value was 0.9. By the ratio of the combination of the above monomer and the monomer of -0.6 or less, gelation can be suppressed even when the unsaturated bond amount is considerably large. E that does not fall within the above range
In the case of a combination of monomers depending on the value, the above-mentioned effect is low.

The side chain used here is a side chain component having a radical polymerizable monomer having a Qe value of e of 0.9 or more in radical copolymerization, and an e value of -0.6. It is also essential that the mixture is composed of a mixture in which the following combinations of monomers are indispensable, and that an aromatic radical-polymerizable monomer is included in the components. As a result of repeated studies on the cause of deterioration of various physical properties, particularly mechanical properties, water resistance, etc., by modification, the resins to be modified are aromatic polyesters and polyester polyurethanes (hereinafter abbreviated as base resins). In this case, depending on the composition of the side chain, its mechanical properties change, and particularly when an aromatic radical-polymerizable monomer is used as a component of the side chain and the compatibility between the main chain and the side chain is increased, We have found that the deterioration of mechanical properties is significantly suppressed. When no aromatic radical-polymerizable monomer is used as the side chain, the compatibility between the main chain and the side chain is low, and among the various physical properties, particularly the elongation of the coating film is significantly reduced.

Further, the inventors of the present invention have repeatedly studied each item such as selection of a reaction solvent for grafting, an initiator, a polymerizable monomer and the like, and finally, the purpose of the present invention is 1). Adhesiveness to various base materials, boiling water resistance, under various additive formulations and application conditions used in the field of application of
It exhibits retort resistance, coating film hardness, gloss, stain resistance, etc., and is extremely high in suppressing deterioration of various physical properties of the base resin, especially mechanical properties and adhesion to various substrates. The present invention has been reached as a rational manufacturing process that is both satisfactory in level and can withstand industrial practice. Each requirement will be described in more detail below.

(Polyester resin) The polyester in the present invention means that the aromatic dicarboxylic acid component is 6% of the total acid component.
It is a polyester containing 0 mol% or more, and its preferable composition is 0.5 to 20 mol% with respect to the total dicarboxylic acid component or the total glycol component of dicarboxylic acid or / and glycol having a polymerizable unsaturated double bond. It is a copolymerized polyester. It is 0 to 40 mol% of an aliphatic and / or alicyclic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like.

As the aliphatic dicarboxylic acid, succinic acid,
Examples thereof include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. Examples thereof include cyclohexanedicarboxylic acid and its acid anhydride.

The dicarboxylic acid having a polymerizable unsaturated double bond includes fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and unsaturated double bond as α, β-unsaturated dicarboxylic acids. Examples of the alicyclic dicarboxylic acid include 2,5-norbornene dicarboxylic acid anhydride and tetrahydrophthalic anhydride. The most preferred of these are fumaric acid, maleic acid, itaconic acid and 2,5-norbornene dicarboxylic acid anhydride.

Further, p-hydroxybenzoic acid, p- (2
-Hydroxyethoxy) benzoic acid or hydroxycarboxylic acids such as hydroxypivalic acid, γ-butyrolactone and ε-caprolactone can be used if necessary.

On the other hand, the glycol component is composed of an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol having 6 to 12 carbon atoms and / or an ether bond-containing glycol. Examples of the aliphatic glycols having a number of 2 to 10 include ethylene glycol and 1,2-propylene glycol.
1,3-propanediol, 1,4-butanedio-
1,5-pentanediol, neopentylglycol
1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, hydroxypivalic acid neopentyl glycol ester, dimethylolheptane and the like can be mentioned, and alicyclic glycos having 6 to 12 carbon atoms. -, As 4-l, 1,4-cyclohexanedimethano-
And tricyclodecane dimethylol.

As the ether bond-containing glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and ethylene oxide or propylene oxide are added to the two phenolic hydroxyl groups of the bisphenols. Examples thereof include glycols obtained by adding one to a few moles of each, such as 2,2-bis (4-hydroxyethoxyphenyl) propane. Polyethylene glycol, polypropylene glycol and polytetramethylene glycol can also be used if necessary.

The polyester resin used in the present invention is
When a dicarboxylic acid having a polymerizable unsaturated double bond is used as the dicarboxylic acid component in an amount of 0.5 to 20 mol% based on the total acid component, the aromatic dicarboxylic acid is 60 to 99.5 mol%, preferably 70 to 99 mol%, 0-40 mol% of aliphatic dicarboxylic acid, and / or alicyclic dicarboxylic acid
However, it is preferably 0 to 30 mol%. When the amount of the aromatic dicarboxylic acid is less than 60 mol%, the processability of the coating film and the blistering resistance and blister resistance of the coating film after the retort treatment are deteriorated. Further, when the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid exceeds 40 mol%, not only the hardness, stain resistance and retort resistance are deteriorated, but also the aliphatic ester bond is more resistant to hydrolysis than the aromatic ester bond. Since the degradability is low, problems such as a decrease in the polymerization degree of the polyester during storage may occur.

The dicarboxylic acid having a polymerizable unsaturated double bond is 0.5 to 20 mol%, preferably 1 to 12
Mol%, and more preferably 1 to 9 mol%. When the dicarboxylic acid having a polymerizable unsaturated double bond is less than 0.5 mol%, effective grafting of the acrylic monomer composition to the polyester resin is not performed, and only the radical polymerizable monomer composition is used. A homopolymer is mainly produced and the target modified resin cannot be obtained.

When the dicarboxylic acid having a polymerizable unsaturated double bond exceeds 20 mol%, various physical properties are largely deteriorated, and the viscosity increases too much in the latter stage of the grafting reaction and the reaction is spread to a stirrer and the reaction becomes uniform. It is not desirable because it hinders progress.

Examples of the glycol having a polymerizable unsaturated double bond include glycerin monoallyl ether, trimethylolpropane monoallyl ether and pentaerythritol monoallyl ether.

When a glycol containing a polymerizable unsaturated double bond is used, its ratio to the total glycol component can be 0.5 to 20 mol%, but preferably 1
˜12 mol%, and more preferably 1 to 9 mol%. When the total amount of the glycol having a polymerizable unsaturated double bond and the dicarboxylic acid is less than 0.5 mol%, effective grafting of the radically polymerizable monomer composition to the polyester resin is not performed, resulting in radically polymerizable A homopolymer consisting only of the monomer composition is mainly produced, and the intended modified resin cannot be obtained.

To introduce a polymerizable unsaturated bond into the polyester, a dicarboxylic acid or / and a glycol is used. The total amount of the glycol having a polymerizable unsaturated double bond and the dicarboxylic acid is up to 20 mol%. When it exceeds 20 mol%, various physical properties are largely deteriorated, and the viscosity is too high in the latter stage of the grafting reaction, and the viscosity is spread to a stirrer and the uniform progress of the reaction is hindered.

In the polyester resin used in the present invention, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol is copolymerized, but the trifunctional or higher polycarboxylic acid is (anhydrous). Trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid,
Trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) and the like are used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as the trifunctional or higher functional polyol. The tricarboxylic or higher functional polycarboxylic acid and / or polyol is 0 relative to the total acid component or the total glycol component.
˜5 mol%, desirably 0.5 to 3 mol%, but if it exceeds 5 mol%, sufficient processability cannot be imparted.

The polyester resin used in the present invention has a weight average molecular weight in the range of 5,000 to 100,000,
The weight average molecular weight is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. When the weight average molecular weight is 5,000 or less, various physical properties are deteriorated, and when the weight average molecular weight is 100,000 or more, the viscosity becomes high during the grafting reaction, which hinders the uniform progress of the reaction.

(Polyurethane Resin) The polyurethane resin in the present invention comprises a polyester polyol (a), an organic diisocyanate compound (b), and optionally a chain extender (c) having an active hydrogen group, and has a weight average molecular weight of Is 5,000 to 100,000, and the urethane bond content is 50
0 to 4000 equivalent / 10 ⁶ g, and the polymerizable double bond content is 1.5 to 30 on average per chain. The polyester polyol (a) used in the present invention is produced by using the compounds already exemplified in the section of polyester resin as the dicarboxylic acid component and the glycol component, and the both end groups are hydroxyl groups and the weight average molecular weight is 500 to 10,000. Is desirable. As in the case of the polyester resin, the polyester polyol used in the present invention has an aromatic dicarboxylic acid component of at least 60 mol% or more, preferably 70 mol% or more.

An aliphatic polyester polyol widely used for general polyurethane resins, for example, a polyurethane resin using an adipate of ethylene glycol or neopentyl glycol has extremely low water resistance. As an example,
The reduced viscosity retention rate after 20 days of immersion in 70 ° C warm water is 20
It is as low as ~ 30%, whereas in the case of a resin having the same glycol terephthalate and isophthalate as polyester polyol, the reduced viscosity retention rate under the same conditions is 80-90%.
And high. Therefore, for high water resistance of the coating film, it is necessary to use a polyester polyol mainly containing an aromatic dicarboxylic acid. Further, polyether polyol, polycarbonate diol, polyolefin polyol and the like can be used together with these polyester polyols, if necessary.

Examples of the organic diisocyanate compound (b) used in the present invention include hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, p-xylylene diisocyanate and m-xylylene diisocyanate. , 1,3-diisocyanate methylcyclohexane, 4,4′-diisocyanate dicyclohexane,
4,4'-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-
Naphthalene diisocyanate, 3,3'-dimethyl-
4,4'-biphenylene diisocyanate, 4,4'-
Examples include diisocyanate diphenyl ether and 1,5-naphthalene diisocyanate.

In the present invention, the chain extender (c) having an active hydrogen group which is optionally used is, for example, ethylene glycol, propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propane. Examples thereof include glycols such as diol, diethylene glycol, spiroglycol and polyethylene glycol, and amines such as hexamethylenediamine, propylenediamine and hexamethylenediamine.

The polyurethane resin used in the present invention includes polyester polyol (a), organic diisocyanate (b),
And a chain extender (c) having an active hydrogen group, if necessary, at a ratio of active hydrogen group / isocyanate group of (a) + (c) of 0.
It is necessary that the polyurethane resin is obtained by reacting at a compounding ratio of 4 to 1.3 (equivalent ratio).

When the ratio of active hydrogen groups / isocyanate groups of (a) + (c) is out of this range, the urethane resin cannot have a sufficiently high molecular weight and desired coating film physical properties can be obtained. Absent. The polyurethane resin used in the present invention is produced by a known method in a solvent at a reaction temperature of 20 to 150 ° C. in the presence of a catalyst or without a catalyst. As the solvent used at this time, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used. As the catalyst for accelerating the reaction, amines, organic tin compounds and the like are used.

The polyurethane resin used in the present invention has a polymerizable double bond in an average of 1.5 per urethane chain in order to increase the efficiency of the grafting reaction with the radical polymerizable monomer.
It is necessary to contain 30 to 30, preferably 2 to 20, and more preferably 3 to 15.

Regarding the introduction of the polymerizable double bond, there are the following three methods: 1) An unsaturated dicarboxylic acid such as fumaric acid, itaconic acid or norbornene dicarboxylic acid is contained in the polyester polyol. 2) An allyl ether group-containing glycol is contained in the polyester polyol. 3) An allyl ether group-containing glycol is used as a chain extender. These can be carried out alone or in combination. The polymerizable double bond in the main chain introduced in 1) has a strong electron accepting property with an e value of 0.9 or more, and the polymerizable double bond introduced in 2) and 3) has an e value of -0.6. It has the following strong electron donating properties.

Considering the size and amount of the electron-accepting property or electron-donating property of the introduced polymerizable double bond in the base resin, the radical-polymerizable monomer also has an electron-donating property. It is an essential point of the present invention to provide for the grafting reaction in consideration of the combination method of the photopolymerizable and electron-accepting monomers and the amount ratio.

The conventional theory for forming a graft or block polymer has been that the number of polymerizable double bonds per main chain is one in the main chain or at the terminal.
In fact, in some of the prior patents, a very narrow range near one is claimed. In the methods of these prior patents, the number of polymerizable double bonds introduced into the main chain is actually incorporated with a statistical distribution, so that the ratio of the chain component which is 0 per main chain increases, This reduces the grafting efficiency. Therefore, if the amount of double bonds is increased, gelation will occur this time, and the appropriate range was extremely narrow. On the other hand, the method of the present invention, which is based on the principle of reaction alternation between radical-polymerizable chemical species, has the advantage that the appropriate range for satisfying the two requirements of high grafting efficiency and avoidance of gelation is wide.

(Radical Polymerizable Monomer) Q-e generally proposed by Alfrey-Price in radical copolymerization
The e value is a value that empirically indicates the electronic state of the unsaturated bond portion of the radically polymerizable monomer, and when there is no significant difference in the Q value, it is considered to be useful for interpreting the copolymerization reaction, and Polymer Ha
ndbook, 3rd ed. John Wiley and Sons.

The radical-polymerizable monomer having an e-value of 0.9 or more, which is always used in the present invention, has an electron-withdrawing substituent in the unsaturated bond portion, and fumaric acid, Fumaric acid monoesters such as monoethyl fumarate, diethyl fumarate and dibutyl fumarate and fumaric acid diesters, maleic acid and its anhydrides, maleic acid monoesters such as monoethyl maleate, diethyl maleate and dibutyl maleate and maleic acid diesters. , Itaconic acid, itaconic acid monoesters and itaconic acid diesters, maleimides such as phenylmaleimide, acrylonitrile, and the like, at least one mixture is used, and most preferably, maleic anhydride and its ester, fumaric acid and These are the esters.

The radical polymerizable monomer having an e-value of -0.6 or less of the Q-e value, which is always used in the present invention, is one having an electron-donating substituent in the unsaturated bond portion, or a conjugated monomer. And vinyl radical polymerizable monomers such as styrene, α-methylstyrene, t-butylstyrene, N-vinylpyrrolidone, vinyl esters such as vinyl acetate, vinyl ethers such as vinyl butyl ether and vinyl isobutyl ether, allyl alcohol, Glycerin monoallyl ether, pentaerythritol monoallyl ether, allyl radical polymerizable monomer such as trimethylolpropane monoallyl ether, a mixture of at least one or more of butadiene is used, and most preferably, such as styrene. It is a vinyl radically polymerizable monomer.

In the present invention, a combination of a radically polymerizable monomer having an e value of 0.9 or more and a radically polymerizable monomer having an e value of -0.6 or less is essential, and at least all radically polymerizable monomers are combined. 50% by weight or more, more preferably 60% by weight
It is preferable that the above is occupied in the combination. Further, with respect to the unsaturated bond contained in the resin to be modified, among the above two kinds of radical polymerizable monomers,
20% by weight or more of the radical-polymerizable monomer having a high copolymerizability (that is, a monomer having a large difference from the e value of the unsaturated bond in the modified resin) in the total radical-polymerizable monomer Radically polymerizable monomer having a low copolymerizability (that is, e of an unsaturated bond in the resin to be modified).
It is preferable that 20% by weight or more of the total radical-polymerizable monomer is contained in the monomer). The former is
If it is less than 20%, sufficient grafting efficiency cannot be obtained with respect to the main chain, and the radically polymerizable monomer will polymerize alone. On the other hand, when the latter is less than 20%, gelation occurs during the graft polymerization, and smooth grafting cannot be performed.

Other radical polymerizable monomers which can be copolymerized with the above-mentioned essential components as required include radical polymerizable monomers having an e value of -0.6 to 0.9. . For example, acrylic acid, methacrylic acid, and ethyl acrylate as their esters,
As a radically polymerizable monomer containing a nitrogen atom, such as methyl methacrylate, one of the monomers that generally contains one radically polymerizable double bond per molecule, such as acrylamide and methacrylonitrile. Alternatively, a plurality of types can be selected and used. This makes it possible to adjust the compatibility of the side chain with Tg and the main chain and to introduce an arbitrary functional group.

As the aromatic radical-polymerizable monomer essential in the side chain component, a radical-polymerizable monomer having an aromatic ring can be mentioned. Styrene, α-methylstyrene, chloromethylstyrene and other styrenes can be used. Derivative, phenoxyethyl acrylate, phenoxyethyl methacrylate,
2-hydroxyethyl acrylate (HEA) such as benzyl acrylate and benzyl methacrylate and 2-
Reaction product of hydroxyethyl methacrylate (HEMA) and aromatic compound, phthalic acid derivative such as 2-acryloyloxyethyl hydrogen phthalate and HEA, H
An ester of EMA, or a reaction product of acrylic acid, methacrylic acid and phenylglycidyl ether, that is,
An aromatic ring can be introduced into the side chain with 2-hydroxy-3-phenoxypropyl (meth) acrylate or the like. In the present invention, the proportion of the aromatic radical-polymerizable monomer used is at least 10% by weight, preferably 20% by weight or more, and most preferably 30% by weight or more, based on the total radical-polymerizable monomers. Preferably there is.

(Grafting Reaction) The graft polymer in the present invention is obtained by graft-polymerizing a radically polymerizable monomer onto the polymerizable unsaturated double bond in the base resin. In the present invention, the graft polymerization reaction is carried out by reacting a radical initiator and a radical-polymerizable monomer mixture in a state where a base resin containing a polymerizable double bond is dissolved in an organic solvent. After the completion of the grafting reaction, the reaction product usually comprises, besides the graft polymer, a base resin which has not been grafted and a homopolymer which has not been grafted with the base resin. Generally, when the ratio of the graft polymer in the reaction product is low and the ratio of the non-graft base resin and the non-graft homopolymer is high, the effect of the modification is low, and as a result, the coating film is not formed by the non-graft homopolymer. Adverse effects such as whitening are observed. Therefore, it is important to select reaction conditions with a high graft polymer formation ratio.

When carrying out the grafting reaction of the radical-polymerizable monomer on the base resin, the radical-polymerizable monomer mixture and the radical initiator are added at once to the base resin dissolved in a solvent while heating. The reaction may be carried out separately, or after dropping separately for a certain period of time, the reaction may be continued by further heating for a certain period of time with stirring. In addition, the radical polymerizable monomer having a small difference from the e value of the polymerizable double bond of the base resin is temporarily added first, and then the difference from the e value of the polymerizable double bond of the base resin is changed. One of the preferred modes of carrying out the present invention is to add a radical-polymerizable monomer having a large amount, and an initiator, dropwise over a certain period of time, and then heat the mixture under stirring for a certain period of time to allow the reaction to proceed.

Prior to the reaction, the base resin and the solvent are charged into the reactor, and the temperature is raised with stirring to dissolve the resin. The weight ratio of base resin to solvent is preferably in the range of 70/30 to 30/70. In this case, the weight ratio considers the reactivity and solvent solubility of the base resin and the radically polymerizable monomer,
During the polymerization process, the weight ratio is adjusted so that the reaction can be carried out uniformly. The grafting reaction temperature is preferably in the range of 50 to 120 ° C. A desirable weight ratio of the base resin and the radical-polymerizable monomer suitable for the purpose of the present invention is in the range of 25/75 to 99/1 in terms of base resin / side chain portion,
The most desirable range is 50/50 to 95/5. When the weight ratio of the base resin is 25% by weight or less, the above-described excellent performance of the base resin, that is, high processability, excellent water resistance, and adhesion to various substrates cannot be sufficiently exhibited. When the weight ratio of the base resin is 99% by weight or more, the ratio of the non-grafted base resin in the graft product is almost the same, and the modification effect is low, which is not preferable.

The weight average molecular weight of the graft chain portion in the present invention is from 1000 to 100,000. When performing graft polymerization by radical reaction, it is generally difficult to control the weight average molecular weight of the graft chain portion to 1000 or less, the grafting efficiency decreases, and the functional group is not sufficiently added to the base resin. Not preferable. Further, when the weight average molecular weight of the graft chain portion is 100,000 or more,
The viscosity increases greatly during the polymerization reaction, making it impossible to carry out the desired polymerization reaction in a homogeneous system. The control of the molecular weight described here can be carried out by appropriately combining the amount of the initiator, the dropping time of the monomer, the polymerization time, the reaction solvent, the monomer composition, or a chain transfer agent or a polymerization inhibitor if necessary.

(Radical Initiator) Well-known organic peroxides and organic azo compounds can be used as the radical polymerization initiator used in the present invention. That is, benzoylperoxide and t-butylperoxide are used as organic peroxides.
Oxypivalate, 2,2'-azobisisobutyronitrile as an organic azo compound, 2,2'-azobis (2,2
4-dimethylvaleronitrile) and the like can be exemplified.

Regarding the selection of the radical initiator compound,
It is necessary to consider the radical generation rate of the compound at the reaction execution temperature, that is, the half-life. Generally, it is desirable to select a radical initiator having a half-life value at that temperature in the range of 1 minute to 2 hours. The amount of the radical initiator used for carrying out the grafting reaction should be at least 0.2% by weight, preferably 0.5% by weight or more, based on the radically polymerizable monomer.

Addition of a chain transfer agent such as octyl mercaptan, dodecyl mercaptan, mercaptoethanol is also used as necessary for adjusting the graft chain length. In that case, it is desirable to add the radically polymerizable monomer in an amount of 0 to 20% by weight.

(Reaction Solvent) As the reaction solvent, general-purpose solvents such as ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate are used. it can. However, the selection of the reaction solvent used in the grafting reaction is extremely important. The conditions to be satisfied as a desirable reaction solvent are 1) solubility, 2) suitability as a radical polymerization solvent, 3) boiling point of the solvent, and 4) solubility of the solvent in water. Regarding 1), it is important to dissolve or disperse the base resin and at the same time to dissolve the branched portion of the graft polymer composed of the unsaturated monomer mixture and the non-grafted homopolymer as well as possible. Regarding 2), the solvent itself must not decompose the radical initiator (induced decomposition), or be a combination that causes an explosive hazard as reported between a specific organic peroxide and a specific ketone solvent. Further, it is important to have an appropriately small chain transfer constant as a reaction solvent for radical polymerization. Regarding 3), since the radical addition reaction of the radically polymerizable monomer is generally an exothermic reaction, it is desirable to carry out under the reflux condition of the solvent in order to keep the reaction temperature constant. Regarding 4), it cannot be said that the grafting reaction itself is an essential requirement, but when the purpose is to introduce a hydrophilic functional group into the base resin by modification and disperse the modified resin in water, From the viewpoint of practical implementation, it is desirable that the solvent selected under the requirements of 1) to 3) is an organic solvent that can be freely mixed with water, or that the water and the organic solvent have high mutual solubility. . When the fourth requirement is satisfied, a water dispersion may be formed by directly adding water to the graft reaction product containing the solvent in a heated state, after neutralization with the basic compound. . More desirable is when the free-mixing or highly mutually-soluble organic solvent has a boiling point lower than that of water. In that case, the organic solvent can be removed to the outside of the system by simple distillation in the water dispersion formed as described above.

The grafting reaction solvent for carrying out the present invention may be a single solvent or a mixed solvent. Those having a boiling point of more than 250 ° C. are not suitable because the evaporation rate is too slow and they cannot be sufficiently removed by baking the coating film at a high temperature. When the boiling point is 50 ° C or lower and the grafting reaction is carried out using it as a solvent,
Since an initiator that is cleaved into radicals at a temperature of 50 ° C. or lower must be used, the handling risk increases, which is not preferable.

The reaction solvent which can be used in the graft reaction when the resulting graft product is intended to be dispersed in water is a solvent which dissolves or disperses the base resin, and is capable of reacting the radical-polymerizable monomer mixture and its polymer. Preferred solvents which are relatively soluble include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclic ethers such as tetrahydrofuran, dioxane, glycol ethers such as propylene glycol methyl ether, propylene glycol propyl ether. , Ethylene glycol ethyl ether, ethylene glycol butyl ether, carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol, glycols or lower esters of glycol ethers such as Chirenguriko - Rujiasete - DOO, ethylene glycol ethyl ether acetate, ketones alcohols e.g. diacetone alcohol, more N-
Substituted amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be exemplified.

When the grafting reaction is carried out in a single solvent, one kind can be selected from the organic solvents in which the base resin is well dissolved. When carrying out in a mixed solvent, the reaction may be carried out by selecting plural kinds only from the above organic solvents.
Alternatively, at least one kind is selected from the organic solvents that dissolve the above base resin well, and at least one kind is selected from organic solvents such as lower alcohols, lower carboxylic acids, and lower amines that hardly dissolve the base resin in the reaction. In some cases, the reaction can be carried out in any solvent.

(Use as Solvent-Soluble Coating Agent) The graft product of the present invention can be used as a solvent-soluble coating agent. As shown in the examples, by increasing the compatibility between the base resin and the graft side chain, the physical properties of the coating film obtained from the graft product are significantly improved. The reason for this is unknown at present, but the mechanical properties of the coating film of the graft product obtained in the combination having poor compatibility are observed to have a large decrease in elongation at break as compared with the base resin. While the processability of the coating film decreases by increasing the compatibility between the main chain and side chains, the decrease in elongation is suppressed, and the decrease in water resistance is hardly observed. It was discovered that it is not different from the upper base resin. Further, it was confirmed that this principle is applicable not only to a heat-dried coating film but also to a baking coating film containing a cross-linking agent, and is applicable to both solvent-soluble type and water-dispersed type. In addition, regardless of the composition of the side chain, it has been observed that the blocking resistance of the heat-dried coating film after grafting is improved from that of the base resin, and a coating film having excellent mechanical properties and blocking resistance of the coating film is observed. In order to obtain a polyester resin or a polyurethane resin whose main chain is an aromatic raw material, an aromatic radical-polymerizable monomer is contained in the side chain component to increase the compatibility of the main chain-side chain. It is necessary to design an improved graft product.

Here, the compatibility is determined by synthesizing the main chain polymer and the side chain polymer independently, dissolving them in an appropriate solvent, and then mixing the polymer solutions of both.
This can be done by observing the turbidity of the film formed therefrom. When a highly transparent film is provided, the compatibility of the main chain polymer and the side chain polymer is good. The graft body of the present invention can be used as it is,
By blending a cross-linking agent (curing resin) and performing bake curing, higher solvent resistance, water resistance and hardness can be exhibited as compared with the base resin. In this case, in the polyester or polyurethane as the base resin, the crosslinkable functional group that can be introduced into the side chain is limited due to its synthetic principle, and three-dimensionalization can be achieved only by using the terminal functional group of the molecule. However, there is a limit in increasing the crosslink density. However, in the graft body of the present invention, since the functional group that can be introduced into the side chain is arbitrary depending on the side chain composition, it is possible to significantly increase the crosslink density as compared with the case where the base resin is crosslinked, and a higher degree of It has been found that solvent resistance, water resistance, and hardness can be imparted.

(Use as water-dispersed coating agent)
The grafting reaction product in the present invention can be water-dispersed by neutralizing the hydrophilic functional group introduced by grafting with a basic compound or the like. The ratio of the hydrophilic functional group-containing radical polymerizable monomer to the hydrophilic functional group-free radical polymerizable monomer in the radical polymerizable monomer mixture depends on the type of monomer selected and the grafting reaction. The acid value of the grafted product is preferably 200 to 4000 equivalents / 1, although it depends on the weight ratio of the base resin / side chain part to be used.
0 ⁶ g, more preferably 500 to 4000 equivalents / 10 ^6.
It is g. As the basic compound, a compound that volatilizes during coating film formation or bake-curing with a curing agent is desirable,
Ammonia and organic amines are suitable. Examples of desirable compounds include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, Diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, tri Examples thereof include ethanolamine. The basic compound has a pH value of the aqueous dispersion of 5.0 to 9.0 depending on the content of the carboxyl group contained in the grafting reaction product, due to at least partial neutralization or complete neutralization. It is desirable to use it as it is.

In carrying out the dispersion in water, the solvent contained in the grafting reaction product is removed in advance by an extruder under reduced pressure to form a grafting reaction in a melt form or a solid form (pellets, powder, etc.). It is also possible to prepare an aqueous dispersion by throwing the product into water containing a basic compound and stirring under heating, but most preferably, the basic compound and water are immediately added at the time when the grafting reaction is completed. Further, a method (one-pot method) of further continuing heating and stirring to obtain an aqueous dispersion is preferable. In the latter case, a part or all of the water-miscible solvent used in the grafting reaction can be removed by distillation or azeotropic distillation with water, if necessary.

(Formulation) The graft product according to the present invention is used as a vehicle for paints, inks, coating agents, adhesives, etc., or as a processing agent for fibers, films and paper products. The graft product of the present invention can be used as it is, but by adding a cross-linking agent (curing resin) and performing bake curing, high solvent resistance,
It can exhibit water resistance and hardness. Examples of the crosslinking agent include phenol formaldehyde resin, amino resin, polyfunctional epoxy compound, polyfunctional isocyanate compound and various blocked isocyanate compounds thereof, and polyfunctional aziridine compound. Examples of the phenol resin include formaldehyde condensation products of alkylated phenols and cresols.
Specifically, alkylated (methyl, ethyl, propyl, isopropyl, butyl) phenol, p-tert-amylphenol, 4,4'-sec-butylidenephenol, p-tert-butylphenol, o-, m-, p -Cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-
Formaldehyde condensates such as nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o-cresol, p-phenylphenol and xylenol can be mentioned.

Examples of amino resins include formaldehyde adducts such as urea, melamine and benzoguanamine,
Further, an alkyl ether compound containing an alcohol having 1 to 6 carbon atoms can be mentioned. Specifically, methoxylated methylol urea, methoxylated methylol
N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, but preferably methoxylated methylol melamine, butoxylated methylol melamine, and methylol Benzoguanamine, which can be used alone or in combination.

Bisphenol A as an epoxy compound
Diglycidyl ether and its oligomer, hydrogenated bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid Acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol di Glycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid tri Lycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct And so on.

Further, as the isocyanate compound, there are aromatic and aliphatic diisocyanates and polyisocyanates having 3 or more valences, and either low molecular weight compounds or high molecular weight compounds may be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimer of these isocyanate compounds, and excess of these isocyanate compounds. The amount of the low molecular weight active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols, polyamides Conflicts with high molecular weight active hydrogen compounds It includes terminal isocyanate group-containing compounds obtained by.

The isocyanate compound may be a blocked isocyanate. Examples of the isocyanate blocking agent include phenol, thiophenol,
Methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol and other phenols, acetoxime, methylethylketoxime, cyclohexanone oxime and other oximes, methanol, ethanol, propanol, butanol and other alcohols, ethylene chlorohydrin, 1, Halogen-substituted alcohols such as 3-dichloro-2-propanol, t
-Tert-alcohols such as butanol and t-pentanol, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propyllactam, and other aromatic amines, imides, acetylacetone, Examples also include active methylene compounds such as acetoacetic acid ester and malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds such as sodium bisulfite. The blocked isocyanate is obtained by subjecting the above isocyanate compound, an isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

A curing agent or an accelerator may be used in combination with these crosslinking agents. The method of blending the cross-linking agent includes a method of mixing with the base resin, and further, there is a method of dissolving it in an organic solvent solution of the graft product in advance and dispersing the mixed solution in water. Can be selected. The curing reaction is generally carried out by adding 5 to 40 parts (solid content) of the curing resin to 100 parts (solid content) of the graft product of the present invention, in the temperature range of 60 to 250 ° C. depending on the type of the curing agent. It is performed by heating for about 60 minutes. If necessary, a reaction catalyst and a promoter are also used in combination. The graft product of the present invention can be blended with pigments, dyes, various additives and the like. The graft product of the present invention can be used as a mixture with other resins, and its processability can be improved.

Further, paints, inks, coating agents, adhesives and various processing agents based on the graft product according to the present invention include dip coating method, brush coating method, roll coating method, spraying method and various printing methods. It has applicability to all.

[0066]

EXAMPLES The present invention will be described below with reference to examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight". Each measurement item followed the following method. (1) Dissolve 0.005 g of weight average molecular weight resin in 10 cc of tetrahydrofuran,
PC-LALLS device Low angle light scattering photometer LS-8000 (manufactured by Tosoh Corporation, tetrahydrofuran solvent, reference: polystyrene) was used for measurement. (2) Glass transition temperature (Tg) The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) at a temperature rising rate of 20 ° C / min. As a sample, 5 mg of the material was put into an aluminum pressing lid type container and crimped before use.

(3) Measurement of Weight Average Molecular Weight of Graft Side Chain The product obtained by graft polymerization was subjected to hydrolysis of the copolyester under reflux in a KOH / water-methanol solution. The decomposition product was extracted with THF under acidic conditions, and the acrylic polymer was purified by reprecipitation with hexane. This polymer was measured with a GPC apparatus (manufactured by Shimadzu Corporation, tetrahydrofuran solvent, converted to polystyrene), and the weight average molecular weight of the graft side chain was calculated. (4) Aqueous dispersion particle size The aqueous dispersion has a solid content concentration of 0.1% by weight using ion-exchanged water.
Adjust the laser light scattering particle size distribution meter Coulter model N
4 (manufactured by Coulter) at 20 ° C.

(5) Aqueous Dispersion B Type Viscosity The viscosity of the aqueous dispersion is a rotational viscometer (manufactured by Tokyo Keiki Co., Ltd., EM).
Type) and was measured at 25 ° C. (6) Reduced viscosity 0.01 g of a polyester resin was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (weight ratio 6/4) and measured at 30 ° C. (7) Hardness of cured coating film (pencil hardness) The coated surface of the steel plate is a high-grade pencil specified in JIS S-6006,
It was measured according to JIS K-5400. (8) Cured coating gloss The 60 ° reflectance was measured.

(9) Cured coating film Flexibility The coated steel sheet was bent 180 degrees, and cracks generated in the bent portion were observed and judged with a 10 times magnifying glass. 4T indicates a case where cracks do not occur at the bent portion even when four bent sheets having the same plate thickness are sandwiched. (10) Adhesion of cured coating film According to ASTM D-3359. (11) Cured coating film The film was rubbed with a gauze impregnated with solvent resistant xylene, and the number of times until the undercoat appeared was recorded.

(12) Cured coating film 2 parts of melamine resin was added to 100 parts by weight of the water resistant graft product.
5 solid parts, paratoluene sulfonic acid (catalyst) 0.25
What mixed the solid part, 100 parts of titanium oxide, and 250 parts of glass beads was shake-dispersed for 5 hours with the paint shaker. Then, it was applied on a zinc iron plate so that the film thickness after drying was 15 μm, and baked at 230 ° C. for 1 minute. The coated plate thus obtained was boiled in boiling water for 2 hours and evaluated by gloss retention (%). The gloss retention rate was calculated by the following formula. Gloss retention rate (%) = (Gloss after treatment / Gloss before treatment) ×
100

(13) Polyester Grafting Efficiency The product obtained by the graft polymerization was analyzed by 220 MHz 1H NMR.
And 55 MHz 13C NMR (Varian, measurement solvent CDCl3 /
The measurement was performed with DMSO-d6), and the grafting efficiency was measured based on the intensity change of the signal derived from the double bond of the double bond-containing component copolymerized with polyester. Polyester grafting efficiency = (1- (relative intensity of signal derived from double bond of double bond-containing component of graft polymerization product / relative intensity of signal derived from double bond of double bond-containing component of raw material polyester)) × 100 (%) The relative intensity was calculated by comparison with the signal intensity of the internal signal as a reference signal.

(14) Evaluation of compatibility between main chain and side chain The resin which becomes the main chain and the resin which becomes the side chain of the graft body were independently synthesized, and each was made into a transparent tetrahydrofuran solution having a solid content concentration of 5%. Then, they were mixed at a solid weight ratio of 50/50, coated on glass so that the film thickness after drying was 100 μm, and dried at 120 ° C. for 10 minutes to obtain a coating film.
The transparency of this coating film was visually evaluated. ◯: The coating film has high transparency Δ: The coating film is cloudy ×: The coating film is whitened

Production Example of Polyester Resin In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 466 parts of dimethyl terephthalate, 466 parts of dimethyl isophthalate, 401 parts of neopentyl glycol, 443 parts of ethylene glycol, and Charge 0.52 parts of tetra-n-butyl titanate,
The transesterification reaction was performed from 160 ° C to 220 ° C over 4 hours. Next, 23 parts of fumaric acid was added and the temperature was raised from 200 ° C to 220 ° C over 1 hour to carry out an esterification reaction. Then raise the temperature to 255 ° C and gradually reduce the pressure in the reaction system.
The reaction was carried out for 1 hour and 30 minutes under a reduced pressure of 0.2 mmHg to obtain polyester (A-1). The obtained polyester (A-1) was light yellow and transparent. The composition measured by NMR and the like was as follows. Dicarboxylic acid component 47 mol% terephthalic acid 48 mol% isophthalic acid 5 mol% Fumaric acid 5 mol% Diol component neopentyl glycol 50 mol% Ethylene glycol 50 mol% Various polyesters shown in Table 1 (A-2
~ 4) were produced. Table 1 shows the molecular weight of each polyester and the composition analysis results measured by NMR and the like. In the table, each component indicates the number of moles.

[0074]

[Table 1]

Production Example of Polyester Polyurethane Resin In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 466 parts of dimethyl terephthalate, 466 parts of dimethyl isophthalate, 401 parts of neopentyl glycol, 443 parts of ethylene glycol, And 0.52 parts of tetra-n-butyl titanate were charged,
The transesterification reaction was performed from 160 ° C to 220 ° C over 4 hours. Next, 23 parts of fumaric acid was added and the temperature was raised from 200 ° C to 220 ° C over 1 hour to carry out an esterification reaction. Then raise the temperature to 255 ° C and gradually reduce the pressure in the reaction system.
React under a reduced pressure of 0.3 mmHg for 1 hour to remove polyester (A
-5) was obtained. The obtained polyester (A-5) was light yellow and transparent. The composition measured by NMR and the like was as follows. Dicarboxylic acid component Terephthalic acid 47 mol% Isophthalic acid 48 mol% Fumaric acid 5 mol% Diol component Neopentyl glycol 50 mol% Ethylene glycol 50 mol% 100 parts of this polyester polyol is equipped with a stirrer, thermometer and partial reflux condenser Into the reactor that was prepared, 100 parts of methyl ethyl ketone was charged and dissolved, then 3 parts of neopentyl glycol, 15 parts of diphenylmethane diisocyanate,
0.02 parts of dibutyltin laurate was charged and reacted at 60 to 70 ° C. for 6 hours. Then, 1 part of dibutylamine was added and the reaction system was cooled to room temperature to stop the reaction. The reduced viscosity of the obtained polyurethane resin (A-6) was 0.52.

By the same method, polyester polyol
(A-7) and polyester polyurethane (A-8) were produced. Table 1 shows the molecular weight of each polyester and the composition analysis result measured by NMR and the like, and Table 2 shows the composition analysis result of each polyester polyurethane measured by the molecular weight and NMR. Each component in Table 1 indicates the number of moles, and each component in Table 2 indicates parts by weight.

[0077]

[Table 2]

Example 1 A reactor equipped with a stirrer, a thermometer, a reflux device and a metering dropping device was placed in a reactor containing 60 parts of polyester resin (A-1) and methyl ethyl ketone.
70 parts, isopropyl alcohol 20 parts, maleic anhydride
6.4 parts and 5.6 parts of diethyl fumarate were added and heated and stirred to dissolve the resin under reflux. After the resin is completely dissolved, a mixture of 8 parts of styrene and 1 part of octyl mercaptan, 1.2 parts of azobisisobutylnitrile dissolved in a mixed solution of 25 parts of methyl ethyl ketone and 5 parts of isopropyl alcohol are added to the polyester solution over 1.5 hours. To each of them, and the reaction was further continued for 3 hours to obtain a graft body (B-1) solution. To this graft solution, add 20 parts of ethanol, and add 30 parts
After reacting with the maleic anhydride in the side chain of the graft body under reflux for minutes, the mixture was cooled to room temperature. Next, 10 parts of triethylamine was added to this to neutralize it, and then ion-exchanged water 160
Parts were added and stirred for 30 minutes. Then, the solvent remaining in the medium was distilled off by heating to obtain a final aqueous dispersion (C-1). The resulting aqueous dispersion is milky white and has an average particle size of 80 nm and 25 ° C.
The B-type viscosity at 50 was 50 cps. The graft efficiency of this graft body was 60%. This water dispersion at 60 ℃ 60
After being left for a day, no change in appearance was observed, and there was no change in viscosity, indicating excellent storage stability. The molecular weight of the side chain of the obtained graft body was 8,000. Apply this water dispersion to the untreated side of the OPP film and apply 1
After drying at 20 ° C. for 2 hours, a heat-dried coating film having a thickness of 50 μm and containing no curing agent was obtained. The graft body (B-1) is shown in Table 3, the water dispersion (C-1) is shown in Table 5, and the coating properties of the water dispersion (C-1) are shown in Tables 6, 7, and 8.
It was shown to.

Example 2 90 parts of polyester resin (A-1) and 50 parts of cyclohexanone were placed in a reactor equipped with a stirrer, a thermometer, a reflux device and a metering dropping device.
Parts, Solvesso 150 40 parts, maleic anhydride 4 parts, and diethyl fumarate 3 parts were added and heated and stirred to dissolve the resin under reflux. After the resin was completely dissolved, a mixture of 3 parts of styrene and 0.1 part of octyl mercaptan and a solution of 0.6 part of azobisisobutylnitrile dissolved in 10 parts of cyclohexanone were added dropwise to the polyester solution over 1.5 hours, and then for another 3 hours. The mixture was reacted and then prepared into a solution having a solid content concentration of 20% to obtain a graft body solution (B-2). Apply this graft solution to the untreated surface side of the OPP film,
After drying at 20 ° C. for 24 hours, a heat-dried coating film having a thickness of 50 μm and containing no curing agent was obtained. The graft body solution (B-2) and its coating film physical properties are shown in Tables 3 and 5, respectively.

Examples 3 to 4 In the same manner as in Example 1, the polyesters (A-1 to
2) was grafted with the composition shown in Table 3 to produce various water dispersions (C-3 to 4) (Table 5).
Apply this aqueous dispersion to the untreated surface side of the OPP film,
It was dried at 120 ° C. for 2 hours to obtain a heat-dried coating film having a thickness of 50 μm and containing no curing agent. The coating properties are shown in Tables 6 and 7,
The results are shown in Table 8.

Examples 5 to 8 In the same manner as in Example 2, polyesters (A-3
~ 4) and the polyester polyurethanes shown in Table 2 (A-6
, 8) was grafted with the composition shown in Table 3 to prepare a solution having a solid content concentration of 20%, and various graft body solutions (B-5 to 8) were produced (Table 3). This graft solution is applied to the untreated surface side of the OPP film,
Drying was conducted at 24 ° C. for 24 hours to obtain a heat-dried coating film having a thickness of 50 μm and containing no curing agent. The physical properties of this coating film are shown in Tables 6, 7, and 8.
It was shown to.

Comparative Example 1 75 parts of polyester resin (A-1) and 50 parts of cyclohexanone were placed in a reactor equipped with a stirrer, a thermometer, a reflux device and a metering dropping device.
Part, 40 parts of Solvesso 150 were put and heated and stirred to dissolve the resin under reflux. After the resin was completely dissolved, a mixture of 25 parts of acrylic acid and 0.5 part of octyl mercaptan and a solution of 0.6 part of azobisisobutylnitrile dissolved in 10 parts of cyclohexanone were added dropwise to the polyester solution over 1.5 hours, and then 3 parts were added. After reacting for a time, a solution having a solid content concentration of 20% was prepared to obtain a graft body solution (B-2) (Table 4). The graft efficiency of this graft was 20%, and the molecular weight of the side chain of the graft was 12000. This graft solution is applied to the untreated surface side of the OPP film,
It was dried at 120 ° C. for 24 hours to obtain a heat-dried coating film having a thickness of 50 μm and containing no curing agent. The physical properties of this coating film are shown in Tables 6 and 7.
It was shown to.

Comparative Examples 2-4 In the same manner as in Example 1, various polyesters (A-2-
4) was grafted with the composition shown in Table 4 to produce various water dispersions (C-10 to 12) (Table 5).
Apply this aqueous dispersion to the untreated surface side of the OPP film,
It was dried at 120 ° C. for 2 hours to obtain a heat-dried coating film having a thickness of 50 μm and containing no curing agent. The coating properties are shown in Table 6.

Comparative Examples 5 to 6 Polyester polyurethanes (A-6 to 8) in Table 2 were grafted with the composition shown in Table 4 in the same manner as in Example 2 to prepare a solution having a solid content concentration of 20%. Then, various graft body solutions (B-13 to 14) were produced. This graft solution is applied to the untreated side of the OPP film,
After drying for 24 hours, a heat-dried coating film having a thickness of 50 μm and containing no curing agent was obtained. The coating properties are shown in Tables 6 and 7.

Examples 9 to 10 To 100 solid parts of each of the aqueous dispersion (B-1) and the graft solution (B-5), 25 solids of melamine resin (Sumimar M40W, manufactured by Sumitomo Chemical Co., Ltd.) were used. Parts, titanium oxide 125 parts, and glass beads 250 parts were mixed and shaken and dispersed with a paint shaker for 5 hours. Then, it was applied on a zinc iron plate so that the film thickness after drying would be 15 μm, and baked at 230 ° C. for 1 minute to obtain a cured coating film. The coating properties are shown in Table 9.

Comparative Examples 7 to 8 Graft solution (B-9) and (B-1) shown in Table 4
3) Each of 100 solid parts was mixed with 25 solid parts of melamine resin (Sumimar M40S, manufactured by Sumitomo Chemical Co., Ltd.), 125 parts of titanium oxide and 250 parts of glass beads, and shaken with a paint shaker for 5 hours. Finally dispersed. Then, the film thickness after drying on the zinc-iron plate is 15μ
It was applied so as to have a thickness of m and baked at 230 ° C. for 1 minute to obtain a cured coating film. The coating properties are shown in Table 9.

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

[Table 6]

[0091]

[Table 7]

[0092]

[Table 8]

[0093]

[Table 9]

1. The graft product of the present invention has extremely high mechanical properties (elongation at break of heat-dried coating film) and water resistance of a non-grafted base resin, as compared with conventional graft products having no side chain regulation. It can be kept high (Tables 6 and 7). 2. It is shown that the method for producing a graft product of the present invention suppresses an increase in viscosity and gelation during the grafting reaction as compared with the conventional method, and can obtain a high grafting efficiency. Moreover, it is shown that the actual composition can be brought closer to the charged composition of the graft side chain by utilizing the alternating copolymerizability of the radically polymerizable monomer (Tables 3 to 5).

3. The adhesion of the graft product of the present invention to various substrates not only maintains the properties of the base resin,
The base resin shows good adhesion even to a base material whose adhesion was insufficient (Table 8). 4. The graft product of the present invention also shows improvement in hardness, solvent resistance, etc. while maintaining the processability (flexibility) of the base resin even in the case of a cured coating film obtained by blending a curing agent (Table 9).

The present invention is as described above, and the summary of the present invention is as follows. 1. The main chain contains aromatic dicarboxylic acid among all carboxylic acid components.
A polyester containing 60 mol% or more, or a polyester polyurethane comprising the same, the side chain is a polymer of a radical-polymerizable monomer, and the side chain component has an e value of 0.6 or more in handling Q and e value. It is mainly composed of a radical-polymerizable monomer that requires an electron-accepting monomer and an electron-donating monomer having an e value of -0.6 or less, and has an aromatic radical-polymerizable monomer in the side chain component. A graft reaction product comprising a body.

2. The copolymerized polyester resin forming the main chain has a weight average molecular weight of 5,000 to 100,000,
In addition, the dicarboxylic acid or diol having a polymerizable double bond is added to the total carboxylic acid or diol in an amount of 0.5 to 2
The above graft reaction product containing 0 mol%.

3. The copolymer polyester polyurethane resin forming the main chain has a weight average molecular weight of 5,000 to 1,000.
00, content of urethane bond 500 to 4000 equivalent / 10
^The above graft reaction product, which is ⁶ g and has an average content of polymerizable double bonds of 1.5 to 30 per one molecular chain.

4. The weight ratio of the base resin forming the main chain to the radical polymerizable monomer polymer forming the side chain is 25 /
The above graft reaction product, which is in the range of 75 to 99/1.

5. When the base resin forming the main chain and the radical polymerizable monomer polymer forming the side chain are separately polymerized and mixed in a common solvent and cast, the main chain forms a highly transparent film. The above graft reaction product consisting of side chains.

6. In carrying out the grafting reaction, an electron-accepting or electron-donating radical-polymerizable monomer having a small difference from the e value of the base resin and the polymerizable double bond of the base resin is allowed to coexist in advance in the reaction solvent. To the base resin, the electron-donating or electron-accepting radically polymerizable monomer and the initiator having a large difference from the e value of the polymerizable double bond of the base resin and the initiator are added while heating and stirring for a certain period of time. The method for producing a graft reaction product as described above, wherein the reaction is carried out.

7. A solvent-soluble coating resin composition containing the graft reaction product as a binder.

8. Acid value 200-4000 equivalents / 10 ⁶ g
Which is a water-dispersed coating resin composition in which the above graft reaction product is dispersed in an aqueous medium containing a basic compound.

[0104]

INDUSTRIAL APPLICABILITY The graft reaction product of the present invention is a polymer capable of exhibiting the properties of a graft tablet without impairing the mechanical properties of the base resin before grafting, and is either a solvent type or a water dispersion type. It can be used for paints, inks, adhesives and various coating agents even in molds, and the resulting coating film has excellent appearance, processability, adhesion, water resistance and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hideki Tanaka             2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo             Koki Co., Ltd. (72) Inventor Masakatsu Oguchi             2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo             Koki Co., Ltd. F-term (reference) 4J027 AB01 AB02 AB04 AB05 AB06                       AB07 AB09 AB13 AB15 AB16                       AB17 AB18 AB22 AB23 AB24                       AB25 AB34 BA02 BA04 BA05                       BA13 BA15 CB03 CB09 CC02                       CD08

Claims (2)

[Claims] 1. The main chain contains 60 mol% or more of an aromatic dicarboxylic acid in the total carboxylic acid component, and the glycol component has 2 to 10 carbon atoms and / or 6 to 12 carbon atoms. A polyester containing an alicyclic glycol and / or an ether bond-containing glycol, or a polyester polyurethane having the polyester as a main constituent, the side chain satisfying the following requirements (1) to (2): A graft reaction product, which is a polymer of a satisfactory radically polymerizable monomer. (1) An electron-accepting monomer having an e-value of 0.9 or more and an electron-donating electron having an e-value of -0.6 or less in a Q-e value in a polymer of a radically polymerizable monomer that constitutes a side chain. The total weight of the polymerizable monomer accounts for at least 50% by weight of the total radical-polymerizable monomer. (2) In the polymer of the radical-polymerizable monomer forming the side chain, the aromatic radical-polymerizable monomer accounts for at least 10% by weight of the total radical-polymerizable monomer. 2. A base resin and an electron-accepting or electron-donating radical-polymerizable monomer having a small difference from the e value of the polymerizable double bond of the base resin are allowed to coexist in the reaction solvent in advance. Of the polymerizable double bond of the base resin
A method for producing a graft reaction product, which comprises adding an electron-donating or electron-accepting radically polymerizable monomer having a large difference from the value and an initiator with heating and stirring to react them.