GB2250293A

GB2250293A - Thermosetting coating resin and process for producing the same

Info

Publication number: GB2250293A
Application number: GB9118225A
Authority: GB
Inventors: Mitsuru Nagasawa; Kazuyuki Kuwano; Masataka Muramatsu; Kishiro Azuma; Hiroshi Hibino; Kazuko Nakanishi
Original assignee: Toagosei Co Ltd; Toyota Motor Corp
Current assignee: Toagosei Co Ltd; Toyota Motor Corp
Priority date: 1990-08-24
Filing date: 1991-08-23
Publication date: 1992-06-03
Anticipated expiration: 2011-08-23
Also published as: GB2250293B; JP2796883B2; JPH04103610A; GB9118225D0; DE4127927A1

Description

22502 ?3 THERMOSETTING COATING RESIN AND PROCESS FOR PRODUCING THE SAME

The present invention relates to a thermosetting coating resin particularly, but not exclusively for coating automobiles, household electric appliances, etc., as well as to a process for producing such a thermosetting coating resin.

Conventionally, acrylic coatings have been widely used as a thermosetting coating for automobiles, household electric appliances, etc., because of their excellent weather resistance and appearance.

The acrylic resins constituting the main component of the above acrylic coatings are generally those resins obtained by radicalcopolymerizing an alkyl (meth) acrylate (e.g., butyl acrylate, methyl methacrylate, or butyl methacrylate) with a functional group-containing monomer (e.g., 2hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate). Coatings are obtained by adding, to a solution of the above acrylic resin in an organic solvent, a crosslinking agent such as melamine, polyisocyanate or the like; the coating is applied and then baked to form a strong coating film having a three-dimensionally crosslinked network structure.

As mentioned above, thermosetting acrylic coatings are handled ordinarily in the form of an organic solvent solution. Recently, there has been an increasing requirement of reducing the amount of the organic solvent used in solvent type coatings, in view of environmental protection and resource conservation. As a result thereof, it is proposed to increase the solid content in the coating solution, i.e., develop a coating having a high solid content.

In order to retain good coatability evenlwith a high solid content, it is necessary to keep the viscosity of the coating solution at a certain level or lower. Therefore, various ideas have been proposed in formulation a coating of high solid content, and it is proposed, e.g., to lower the molecular weight of a coating resin used.

When the molecular weight of an acrylic resin used is lowered, however, the proportion of the polymer molecule having no functional group, i.e., the polymer molecule not taking part in formation of a network structure during curing is increased in the acrylic resin; as a result, the coating film obtained therefrom has reduced durability.

In order to solve the above problem, it is proposed to increase the proportion of a functional group-containing monomer in relation to the total monomers used for an intended acrylic resin and also increase the amount of a crosslinking agent (e.g., melamine, or polyisocyanate) in proportion to the increase of said monomer. However, this approach gives an acrylic resin having too high a crosslinking density and resultantly 3 1 a coating film of inferior flexibility and brittleness.

Development of a coating of high solid content is under investigation also using different approaches. As an example, there is a proposal of using a branched polymer as a coating resin.

That is, Japanese patent Post-Exam. Publication No. 64-11076 (Laid-Open No. 60-110702) proposes using, as a coating resin, a branched polymer obtained by reacting a polyfunctional epoxy compound represented 10 by the chemical formula:

R-(O-CH -CH-CH 2 ' 1 / 2)n 0 (R is a hydrocarbon residue of aliphatic type, alicyclic type, aromatic type or the like, and n is an integer of 3-6) with an acrylic polymer having a carboxyl group at one end and having a molecular weight of 1,000- 100,000.

The document mentions that an organic solvent solution of the branched acrylic polymer has a viscosity about 30-50% lower than an organic solvent solution of a straight-chain acrylic polymer having about the same average molecular weight.

However, the number of branches per molecule of the above branched acrylic polymer is restricted by the n of the chemical formula:

R-(O-CH 2 -CH-CH 2)n 0 1, and it is virtually impossible to allow the polymer to have a large number of branches; consequently, a coating of high solid content can be obtained but with a restriction.

Also, a graft copolymer obtained by radicalcopolymerizing a macromolecular monomer having a radical-polymerizable group with an acrylic acid ester, is known as a branched polymer (U.S. Patent No. 3,842, 059). Use of such a graft copolymer as a coating resin is proposed, as mentioned below.

U.S. Patent No. 4,804,732 discloses, as a thermosetting coating resin, a graft copolymer obtained by copolymerizing a polysiloxane macromolecular monomer with an acrylic acid ester monomer. The document mentions that the graft copolymer can give a coating of low viscosity but high solid content. However, the polysiloxane macromolecular monomer is a macromolecular monomer obtained by reacting a polysiloxane having a hydroxyl value of about 50-150 with glycidyl methacrylate at a molar ratio of 2:1 to 1:2, preferably 1:1, and contains polysiloxane molecules each having a plurality of carbon-carbon double bonds derived from glycidyl methacrylate and polysiloxane molecules containing no such double bond.

Japanese Patent Unexamined Laid-Open No. 64-. 245067 discloses a two-pack acrylic urethane coating consisting of (a) an acrylic graft copolymer obtained by using a macromolecular monomer having a radical- 1 polymerizable group at one end and (b) a polyisocyanate compound. Japanese Patent Unexamined Laid-Open No. 63-101462 discloses a room temperature-drying type coating consisting of a similar graft copolymer. In. these inventions, a graft copolymer is used as a coating resin in order to allow the coating film formed therefrom to have improved properties; however, no mention is made of any coating of high solid content. We have now found it possible to provide a thermosetting coating resin comprising a cross linkable branched polymer capable of providing a coating solution of high solid content but low viscosity, and to provide a process for producing such a resin.

The present inventors made extensive studies in order to solve the above-mentioned problems and, as a result, found that a branched polymer which is obtained from a radical-polymerizable macromolecular monomer having a weight-average molecular weight of 1,000- 10,000 and which contains the unit of said macromolecular monomer in a proportion of 40% by weight or more based on the amount of the total constitutional units and has a weight-average molecular weight of 5,000- 30,000, gives a low viscosity when made into an organic solvent solution of high solid content.

1) r_ According to one aspect of the present invention there is provided a thermosetting coating resin consisting of a branched polymer, which branched polymer is obtained by copolymerizing a macro- 1 molecular monomer having a radical-polymerizable group at one end in the molecule and having a weight-average molecular weight of 1,000-10,000, with another radicalpolymerizable monomer, which branched polymer contains the unit of said macromolecular monomer in a proportion of 40-99. 5% by weight based on the amount of the total constitutional units, which branched polymer has a crosslinkable functional group, and which branched polymer has a weight-average molecular weight of 10 5,000-30,000.

According to another aspect of the present invention there is provided a process for producing a thermosetting coating resin having a crosslinkable functional group in the molecule and having a weight- average molecular weight of 5,000-30,000, which process comprises subjecting polymerizable components (c) to radical copolymerization-by using 1-10 mole %, based on the total moles of the polymerizable components (c), of a radical polymerization initiator, said polymerizable components (c) consisting of 40-99.5% by weight 20 of (a) a macromolecular monomer having a radicalpolymerizable group at one end in the molecule and having a weight-average molecular weight of 1,000-10,000 and 60-0.5% by weight of (b) another radical-polymerizable monomer.

Various preferred features and embodiments of the present invention will now be described by way of non-limiting example.

1 [Macromolecular monomer] The macromolecular monomer used in the present invention is, as mentioned above, a highmolecular monomer having a weight-average molecular weight of 1,000-10,000 and having a radical-polymerizable group at one end in the molecule. Theradical polymerizable group may be a (meth) acryloyl group, styryl group, allyl group, vinylbenzyl group, vinyl ether group, vinyl ketone group, etc.

Among them (meth)acryloyl group is preferred.

The above weight-average molecular weight of the macromolecular monomer is obtained by a method ordinarily used in the measurement of weight- average molecular weight of a polymer, for example, gel permeation chromatography (hereinafter referred to as GPC) or smallangle light- scattering method. When the weight-average molecular weight of the macromolecular monomer is more than 10,000, the resulting branched polymer has too large a molecular weight and, when made into a solution, has too high a viscosity, which gives poor coatability. Meanwhile, when the weight-average molecular weight of the macromolecular monomer is less than 1,000, the resulting branched polymer gives a high solution viscosity, which makes it impossible to obtain a coating of high solid content. The preferable weight-average molecular weight of the macromolecular monomer is 1,000-5,000.

The monomer constituting the polymer backbone 1 of the macromolecular monomer, i.e., the monomer constituting the moiety supporting the radical-polymerizable group of the macromolecular monomer, may b! methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2- ethylhexyl perfluoroalkyl acrylates, 2-hydroxyethyl (meth)acrylate, (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, a-methylstyrene (meth)acrylonitrile, polyethylene glycol mono(meth)acrylate, etc. These monomers can be used alone or in combination of two or more.

The polymer backbone of the macromolecular monomer preferably has a crosslinkable functional group as mentioned later, such as hydroxyl group or carboxyl group.

The macromolecular monomer can be synthesized by various methods such as the methods described in the second chapter (synthesis of macromolecular monomer) (pages 39-77) of "Chemistry and Industry of Macromolecular Monomer" (edited and written by Yuya Yamashita) published from I. P. C. Publishing on Sept. 20, 1989.

That is, the macromolecular monomer can be synthesized, for example, by a method which comprises subjecting an anion-polymerizable monomer (e.g., styrene) to solution polymerization in the presence of an anion polymerization initiator (e.g., butyllithium) to prepare a monofunctional living polymer, subjecting the monofunctional living polymer to end capping with ethylene oxide or the like when the molecular weight of the living 1 polymer has reached a desired level, and reacting the reaction product with methacrylic acid chloride or the like to obtain a macromolecular monomer having a radical-polymerizable group (e.g., methacryloyl group) at one end (Japanese Patent Laid-Open No. 51-125186 corresponding to U.S. Patent No. 3,482,059); a method which comprises anion-polymerizing methyl methacrylate in the presence of p-vinylbenzylmagnesium chloride (initiator) at a low temperature to obtain a polymethyl 10 methacrylate macromolecular monomer having a pvinylbenzyl group at one end (Polym. J., 18, p. 581, 1986); and a method which comprises radical-polymerizing a radical-polymerizable monomer [e.g., (meth)acrylic acid ester, styrene, or acrylonitrile] in the presence 15 of a chain transfer agent of carboxyl group-containing mercaptan type (e.g., thioglycolic acid, or mercaPtopropionic acid) in an organic solvent to prepare a polymer having a carboxyl group at one end in the molecule, and reacting the polymer with glycidyl (meth)20 acrylate to obtain a macromolecular monomer having a methacryloyl group at one end in the molecule (Japanese Patent Laid- Open No. 60-133007, etc.).

Further, the macromolecular monomer having carboxyl groups in the polymer backbone can be synthesized by a method which comprises synthesizing a macromolecular monomer having tertiary alkyl ester groups such as t-butyl (meth)acrylate monomer unit or the like, and decomposing the t-butyl carboxylate group in the 1 presence of an acid catalyst into a carboxyl group and isobutylene to form a macromolecular monomer having carboxyl groups.

[Branched polymer] The branched polymer of the present invention is a polymer which consists of a unit of the abovementioned macromolecular monomer and a unit of another radical-polymerizable monomer (the proportion of the macromolecular monomer unit being 40-99.5% by weight based on the amount of the total constitutional units) and which contains a crosslinkable functional group in the molecule and has a weight-average molecular weight of 5,000-30,000. This branched polymer may be a kind of graft copolymer wherein a number of branched polymers derived from the macromolecular monomer have been bonded to a trunk polymer of short chain.

The above-mentioned weight-average molecular weight of the branched polymer is a value measured by small-angle light-scattering method. When the weight- average molecular weight is less than 5,000, such a branched polymer gives a coating film of inferior durability. When the weight-average molecular weight is more than 30,000, such a branched polymer gives a coating solution of high viscosity and accordingly of poor coatability.

When the proportion of the macromolecular monomer unit is less than 40% by weight, such a branched 1 polymer has insufficient branching degree and, when made into a solution of high solid content, gives a high viscosity, which makes it impossible to obtain a practical coating solution of high solid content. When the proporti6n of the macromolecular monomer unit is more than 99.5% by weight, such a branched polymer is difficult to synthesize at a high purity and contains a large amount of non-polymerized macromolecular monomer, which gives a coating film of poor durability. The preferable proportion of the macromolecular monomer unit is 45-95% by weight.

The other radical-polymeriz able monomer to be copolymerized with the macromolecular monomer, may be alkyl (meth)acrylates wherein the alkyl group has 1-18 carbon atoms, vinyl acetate, styrene, a- methylstyrene, (meth)acrylonitrile, perfluoroalkyl (meth)acrylates, (meth)acrylic acid, maleic anhydride, 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, Nmethylolacrylamide, N-butoxymethylacrylamide, N,Ndimethylaminoethyl (meth)acrylate, (meth)acryloyloxypropyltr-4methoxysilane, etc.

It is necessary that the branched polymer have a crosslinkable functional group. The crosslinkable functional group is preferably hydroxyl group, carboxyl group, amino group, glycidyl group, -CONH(CH 20R) (R is hydrogen atom or an alkyl group), or the like - A. hydroxyl group or carboxyl group is more preferable. The 1 crosslinkable functional group which must be present in the branched polymer, may be of two different types. The crosslinkable functional group may be present at the macromolecular monomer portion, tor at the portion of the-trunk polymer formed by the monomer other than the macromolecular monomer, or at the two portions.

In order to introduce the crosslinkable functional group into the trunk polymer portion, there may be used, as the monomer to be copolymerized with the macromolecular monomer, a crosslinkable functional groupcontaining monomer among the above-mentioned monomers, such as (meth)acrylic acid, maleic anhydride, 2hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate or the like. (Meth)acrylic acid or 2-hydroxyethyl (meth)acrylate is preferred.

The preferable amount of the crosslinkable functional group in the branched polymer differs slightly depending on the type of the functional group, but is about 0.5-30% by weight based on the amount of the total monomer units constituting the branched polymer when expressed as the amount of the unit of the crosslinkable functional group-containing monomer.

Preferably, the branched polymer used in the present invention is constituted mainly by the unit of an acrylic monomer typified by a (meth)acrylic acid ester, in view of the weather resistance of the coating film formed therefrom. Specifically, it is preferable that the macromolecular monomer unit or the trunk 1 polymer formed by the other radical-polymerizable monomer contain at least 50% by weight, based on the amount of the total monomer units, of an acrylic monomer unit. The acrylic monomer is preferably methyl (meth)acrylate, ethyl-(meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate or octyl (meth)acrylate.

The branched polymer can be obtained by radicalcopolymerizing the macromolecular monomer and the other radical-polymerizable monomer (these monomers are herein- after referred to as polymerizable components) in an organic solvent.

The organic solvent is preferably toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone or the like. The concentration of the polymerizable components in the solution polymerization is preferably 10- 80% by weight. The polymerization temperature is conveniently about 60- 100'C.

As the polymerization initiator, there can be used an azo type compound such as 2,2-azobisisobutyronitrile (hereinafter referred to as AIEN) or the like, or an organic peroxide such as benzoyl peroxide or the like. The required amount of the initiator is 1-10 moles, preferably 5-10 moles per 100 moles of the total polymerizable components.

The molecular weight of the branched polymer can be effectively controlled by the use of a chain transfer agent in combination with the polymerization initiator. The chain transfer agent, may be 1 dodecyl mercaptan, lauryl mercaptan, thio glycolic acid, etc. The preferable amount of the chain transfer agent used is 1-40 moles per 100 moles of the total polymerizable components.

The branched polymer which is the thermosetting coating resin of the present invention can be cured, for example, by the following methoclt.

The branched polymer having a carboxyl group as the crosslinkable functional group can be cured by heating to 120-160'C in the presence of, as a cross linking agent, an amino resin such as hexamethylol melamine, hexabutoxymelamine or a condensation product thereof.

The branched polymer having a hydroxyl group can be cured at room temperature or under heating, by using, as a crosslinking agent, a polyisocyanate (e.g., hexamethylene diisocyanate, tolylene diisocyanate, or isophorone diisocyanate) or an adduct thereof.

The branched polymer having a glycidyl group can be cured by heating to 80 to 200C using, as a crosslinking agent, a polycarboxylic acid in the presence of a curing accelerator such as tertiary amine, quaternary ammonium salt or the like. It can also be cured at room temperature or under heating, by using a polyamine such as triethylenetetramine as a crosslinking agent.

The amount of the crosslinking agent used can be appropriately determined according to -the known - 15 1 technique.

The branched polymer having N-methylolamide group as the crosslinkable functional group can be self cured by heating and needs no crosslinking agent.

The present invention is hereinafter described more specifically by reference to the following non-limiting Examples. Incidentally, the macromolecular monomers used in the Examples were those obtained in the following Referential Examples.

Referential Example 1 106.2 parts by weight of toluene was fed into a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet. Into the flask was continuously added dropwise a mixed solution consisting of 80 parts by weight of methyl methacrylate (hereinafter referred to as MMA), 20 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 10.6 parts by weight of mercaptoacetic acid as a chain transfer agent and 2 parts by weight of AIBN as a polymerization initiator, at 80850C in 3 hours while nitrogen gas was being blown therein, to carry out polymerization. After the completion of the dropwise addition, the heating was continued further for 2 hours to complete- the polymerization to obtain a polymer having a carboxyl group at one end in the molecule.

A part of the toluene solution of the polymer 1 was taken out and mixed with hexane to precipitate and separate the polymer. The polymer was measured for acid value. The acid value was 0.82 mg equivalent/g.

To the toluene solution of the polymer was added 200 ppm of hydroquinone monomethyl ether as a polymerization inhibitor. To the resultant solution were added glycidyl methacrylate of 1.1 times equivalents the above acid value, and a quaternary ammonium salt as a catalyst, and they were kept at 900C for 6 hours to react the end carboxyl group of the polymer with glycidyl methacrylate. The reactivity calculated from the decrease in acid value was 98.5%. From the above procedure was obtained a macromolecular monomer of MMA/HEMA = 80/20 (weight ratio) having a methacryloyl group at one end in the molecule, and having a polystyrene- reduced number-average molecular weight of 1,340 and a polystyrene- reduced weightaverage molecular weight of 2,600 as measured by GPC.

Referential Example 2 20 The following monomers were radical-polymerized in the same manner as in Referential Example 1 to synthesize a macromonomer precursor, i.e., a polymer having a carboxyl group at one end. Styrene/butyl methacrylate/butyl acrylate/ hydroxyethyl methacrylate = 30/30/20/20 (weight ratio) The polymer was reacted with glycidyl methacrylate to synthesize a macromolecular monomer having.a methacryloyl group at one end in the molecule. It had a number-average molecular weight of 1,220 and a weightaverage moledular weight of 2,060.

Example 1

There was prepared a toluene solution which contained 20% by weight of polymerizable components consisting of the macromolecular monomer obtained in Referential Example 1, styrene and MMA (the weight ratio = 45/25/30) and 8.4 mole %, based on the total moles of the polymerizable components, of AIBN as a polymerization initiator. The solution was subjected to polymerization at 60'C for 8 hours.

The resulting polymer solution was subjected to GPC to determine the amount of non-polymerized macromolecular monomer. The amount was 10% by weight based on the macromolecular monomer fed. As a result, the composition of the branched polymer obtained was found by calculation to consist of 42% by weight of the macromolecular monomer unit, 26% by weight of the styrene unit and 32% by weight of the MMA unit, the styrene unit and the MMA unit constituting the trunk moiety. The branched polymer had a weight-average molecular weight (Mw) as measured by small-angle lightscattering method and a solution viscosity (TI) (a viscosity measured by an Ubbelohde viscometer at 250C 1 for an acetone solution containing 40% by weight of the branched polymer; the same applies hereinafter) as shown below.

Mw: 14,000 Ti: 11. 6 cp Example 2

A branched polymer was produced in the same manner as in Example 1 except that the polymerizable components consisted of 70% by weight of the macromolecular monomer obtained in Referential Example 1, 12% by weight of MMA and 18% by weight of styrene.

GPC analysis of the polymerization product indicated the presence of 10% by weight, based on the macromolecular monomer fed, of non-polymerized macro- molecular monomer. As a result, the composition of the branched polymer obtained was found by calculation to consist of 68% by weight of the macromolecular monomer unit, 13% by weight of MMA unit and 19% by weight of the styrene unit, the MMA unit and the styrene unit constituting the trunk moiety.

The Mw and n of the branched polymer measured in the same manner as in Example 1 were as follows.

Mw: 23,100 fl: 13.2 cp Example 3

There was prepared a toluene solution which T - 19 contained 20% by weight of polymerizable components consisting of 93% by weight of the macromolecular monomer obtained in Referential Example 1 and 7% by weight of styrene, 8.4 mole %, based on the total moles of the polymerizable components, of AIBN as a polymerization initiator, and 7.5 mole %, based on the total moles of the polymerizable components, of lauryl mercaptan as a chain transfer agent. The solution was subjected to polymerization at 601C for 8 hours.

GPC analysis of the polymerization product indicated the presence of 15% by weight, based on the macromolecular monomer fed, of non-polymerized macromolecular monomer, from which the composition of the branched polymer obtained was found to consist of 92% by weight of the macromolecular monomer unit and 8% by weight of the styrene unit.

The Mw and n of the branched polymer were as follows.

MW: 19,000 n: 11. 4 cp Example 4

A branched polymer was produced in the same manner as in Example 3 except that the polymerizable components consisted of 95% by weight of the macromolecular monomer obtained in Referential Example 2 and 5% by weight of butyl methacrylate.

The resulting polymer solution contained 20% - 20 1 by weight, based on the macromolecular monomer fed, of non-polymerized macromolecular monomer. The branched polymer obtained from the solution had a Mw of 23,000 and an n of 12.8 cp.

Comparative Examples 1 and 2 80% by weight of MMA and 20% by weight of HEMA were dissolved in a toluene-isobutanol mixed solvent to prepare a solution having a total monomer concentration of 20% by weight. Thereto were added 8.4 mole %, based 10 on the total moles of the polymerizable components, of AIBN and 4 mole % of lauryl mercaptan (Comparative Example 1), or 8.4 mole % of AIBN and 1 mole % of lauryl mercaptan (Comparative Example 2). The resulting mixture was subjected to the same polymerization as in Example 1.

Each of the resulting straight-chain polymers had the following Mw and n.

Comp. Ex. 1 Comp. Ex. 2 MW n (cp) 14,000 21.2 22,000 70.3 Comparative Example 3 Only the macromolecular monomer obtained in Referential Example 2 was polymerized under the same conditions as in Example 3.

The resulting polymer solution contained 45% 1 by weight, based on the macromolecular monomer fed, of non-polymerized macromolecular monomer. The polymer containing non-polymerized macromolecular monomer had a Mw as low as 4,400 and was not suitable for use in coating.

As clear from the foregoing Examples and Comparative Examples, the resin solutions obtained in Comparative Examples had too high a viscosity and were not suitable for use in coating, while Examples of the present invention easily produced thermosetting coating resins showing a low solution viscosity even at a high concentration, which were -usable to prepare a coating of high solid content.

Cl aims 1. A thermosetting coating resin comprising _ branched polymer, which branched polymer is obtainable by copolymerizing a macromolecular mpnomer having a.

radical-polymerizable group at one end in the molecule _and having a weight-average molecular weight of 1,000 10,000, with a radical-polymerizable monomer, which branched polymer contains the unit of said macromolecular monomer in a proportion of 40-99.5% by weight based on the amount of total constitutional units, which branched polymer has a crosslinkable functional group, and which branched polymer has a weight-average molecular weight of 5,000-30,000.

2. A thermosetting coating resin according to

Claims

Claim 1, wherein the branched polymer contains alkyl (meth)acrylate

monomer having an alkyl group of 1-8 carbon atoms, in a proportion of 50% by weight or more based on the total amount of total monomer constituting the branched polymer.

3. A thermosetting coating resin according to Claim 1 or 2, wherein the branched polymer contains the macromolecular monomer in a proportion of 45-95% by weight.

4. A thermosetting coating resin according to any of Claims 1-3, wherein the crosslinkable functional group in the branched polymer isla hydroxyl group or a carboxyl group.

5. A thermosetting coating resin according to any 1 - 23 of Claims 1-4, wherein the radical-polymerizable group at one end of the macromolecular monomer is selected from a (meth) acryloyl group, styryl group, allyl group, vinylbenzyl group, vinyl ether group or vinyl ketone group.

6. A thermosetting coating resin according to any of Claims 1-5, wherein the monomer constituting the polymer backbone of the macromolecular monomer is selected from -methyl (meth) acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, perfluoroalkyl acrylates, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) acrylate, styrene, a-methylstyrene, (meth)acrylonitrile or polyethylene glycol mono(meth)acrylate.

7. A thermosetting coating resin according to any of Claims 1-6, wherein the other radical-polymerizable monomer is selected from alkyl (meth)acrylate wherein the alkyl group has 1-18 carbon atoms, vinyl acetate, styrene, a-methylstyrene, (meth) acrylonitrile, perfluoroalkyl (meth)acrylate (meth) acrylic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N,N-dimethylaminoethyl (meth) acrylate or (meth)acryloyloxypropyltrimethoxysilane.

8. A process for producing a thermosetting coating resin having a crosslinkable functional group in the molecule and having a weight-average molecular weight of 5,000-30,000, which process comprises subjecting polymerizable components (c) to radical copolymerization using 1-10 mole %, based on the total moles of the polymerizable components (c), of a radical polymerization initiator, said polymerizable components (c) comprising 40-99.5% by weight of (a) a macromolecular monomer having a radical- polymerizable group at one end Or the molecule and having a weight- average molecular weight of 1,000-10,000 and 60-0.5% by weight of (b) a radical-polymerizable monomer.

9. A process for producing a thermosetting coating resin according to claim 8 wherein radical polymerization is in the presence of a chain transfer agent.

10. A process for producing a thermosetting coating resin according to Claim 8 or 9, wherein the proportions of the component (a) and the component (b) in the polymerizable components (c) are 45-95% by weight for the component (a) and 55-5% by weight for the component (b).

11. A process for producing a thermosetting coating resin according to any of Claims 8-10, wherein the thermosetting coating resin contains a unit of an alkyl (meth)acrylate monomer having an alkyl group of 1-8 carbon atoms in a proportion of 50% by - weight or more based on the amount of total monomer units constituting the thermosetting coating resin.

12. A process for producing a thermosetting coating resin according to any of Claims 8-11, wherein the component (a) is a macromolecular monomer having a radical-polymerizable group at one end in the molecule, having a weight-average molecular weight of 1,000-10,000 and having carboxyl group or hydroxyl group in the polymer backbone.

13. A process for producing a thermosetting coating resin according to any of Claims 8-12, wherein the radical polymerizable group at one end of the macromolecular monomer is selected from a (meth) acryloyl group, styryl group, allyl group, vinylbenzyl group, vinyl ether group or vinyl ketone group.

14. A process for producing a thermosetting coating resin according to any of Claims 8-13, wherein the monomer constituting the polymer backbone of the macro molecular monomer is selected from a methyl (meth)acrylate, ethyl (meth)acryate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, perfluoroalkyl acrylates, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, a-methylstyrene, (meth)acrylo nitrile or polyethylene glycol mono(meth)acrylate.

15. A process for producing a thermosetting coating resin according to any of Claims 8-14, wherein the other radical-polymerizable monomer is selected from a alkyl (meth)acrylate wherein the alkyl group has 1-18 carbon atoms, vinyl acetate, styrene, a- methylstyrene, (meth)acrylonitrile, perfluoroalkyl (meth)acrylate, (meth)acrylic acid, maleic anhydride, 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N,Ndimethylaminoethyl (meth)acrylate or (meth)acryloyloxypropyltrimethoxysilane.

1 16. A method of coating an article comprising applying a thermosetting coating resin according to any one 1 of claims 1 to 7 to'said article.

17. An article coated according to the method of claim 16. 18. Use of a resin according to any one of claims 1 to 7 for coating an article.

19. A thermosetting coating resin according to any one of claims 1 to 7 substantially as hereinbefore described.

20. A process for producing a thermosetting coating resin according to any one of claims 8 to 15 substantially as hereinbefore described.

21. A method of coating an article according to claim 16 substantially as hereinbefore described.

22.

described.

23. Use of a resin according to claim 18 substantially as hereinbefore described.

24. Each and every novel compound, composition, product, method and use substantially as hereinbefore described.

An article according to claim 17 substantially as hereinbefore