JPH04209625A - Liquid polymer and polyol composition - Google Patents

Abstract

PURPOSE: To enhance the hardness, impact resistance, weatherability, corrosion resistance, hydrolysis or adhesiveness of an obtd. film or surface coating, by making the composition contain a esterphenol-capped liquid polymer and an amino crosslinking agent.

CONSTITUTION: The compsn. is obtained by compounding a non-liquid crystalline esterphenol-capped polymer (A) represented by formula [wherein R is a polyvalent group with a number average mol.wt. of 200-10,000 derived from a polymer having two or more aliphatic hydroxy groups or epoxy functional groups; R¹ is a direct bond or 1-20C (oxy)hydrocarbylene; R₂ is H, OH, a halogen, 1-4C alkyl or 1-4C alkoxy(carbonyl) and n is 2-10] with a glass transition temp. of -40-40°C, an amino crosslinking agent (B) wherein a ratio of an active crosslinking group of the component B to a phenol group of the component A is 1.0-15.0:1.0 and, if necessary, alkali (alkaline earth) metal salt of weak acid, an acid catalyst or a solvent (C).

COPYRIGHT: (C)1992,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid polymer and polyol compositions, solid crosslinked polymer compositions made therefrom, and methods of improving the coating properties of films and surface coatings.

The invention further relates to the production of phenolic functional end-capped polymers and polyols.

Coating formulations typically include many ingredients.

The first component is the resin, which can be natural or synthetic. The resin acts as a polymer coating binder or as a polymer coating vehicle for the coating formulation. Furthermore, most coatings require solvents, and coatings can further contain a wide variety of additives. Additionally, many coatings contain crosslinking agents, which chemically react with the resin during the curing step after application of the coating vehicle to the substrate to produce a film containing a crosslinked network.

A crosslinked network is necessary to obtain good film properties. The curing step can be carried out at ambient conditions ("air drying system") or at elevated temperature ("baking system").

In both cases, the solvent evaporates during the curing step and a coated film is obtained. Coating films have hardness, flexibility, weather resistance, chemical resistance, solvent resistance,
Many properties are important, including corrosion resistance, adhesion to various substrates, impact resistance, etc.

Properties depend on many factors, including resin type, molecular weight, monomer composition, and glass transition temperature (Tg), as well as type and amount of crosslinker, curing conditions, curing catalyst, and additives. Modification of these parameters can be used to obtain a wide range of different film properties to suit the needs of many different applications. however,
It is not always possible to optimize all desired properties at the same time.

For example, hardness and impact resistance are two desirable properties of a coating, but they are somewhat contradictory properties since high hardness usually results in a film with a high Tg. Conversely, if the material has high impact resistance, the Tg will be low. For this reason,
A trade-off between high hardness and high impact resistance must be considered. Optimizing one of these properties often results in a loss of the other.

Filed March 28, 1988, October 1, 1988
European Patent Application No. 0287233 by Jones et al., published on the 9th, describes a method of simultaneously obtaining high hardness and high 1# impact resistance in coatings by using liquid crystal (L, C,) polymers. Suggested. The L, C, polymer is characterized by containing a mesogenic (+nesogenic) group that imparts liquid crystallinity to the polymer. A mesogenic group is a chemical structure containing at least two, and often more, hard moieties, a rigid array of aromatic rings attached in the rose position by covalent bonds or other rigid or semi-rigid chemical bonds. In addition to the mesogenic groups, the polymers contain conventional polymeric units covalently attached to the mesogen.

Jones blends these glues with suitable crosslinking resins, such as aminoblast resins, to produce coating vehicles that cure by baking to produce films with both high hardness and high impact resistance. ing. The improved properties are due to the interaction of the various polymer chains. Often used mesogens consist of two or more internal esters of p-hydroxybenzoic acid (PHBA). This mesogen is attached to the high molecular weight polyol by esterification of the OH groups of the polyol with the remaining carboxyl groups of the mesogen.

Although the L,C,polymer has good properties, it also has some drawbacks. First, it is usually expensive to synthesize or introduce mesogenic groups into polymers. for example,
Due to the multiple P)IBA end groups, a large amount of P)! 8A is required, which significantly increases the price of the resin. Second, the synthesis is complex. In one method, the synthesis is based on the use of expensive and toxic synchhexylcarbodiimide, which makes the method impractical from a commercial standpoint. Another method is to
-) Based on direct esterification with polyester diols in the presence of luenesulfonic acid (p-TSA).

Jones suggests that it is important to use acid catalysts and control temperature to produce superior C, phenolic oligoesters. however,
Polymers produced by the Jones technique have poor color properties, unacceptably high loss of PH8A due to dicarboxylation, and significant loss of phthalic acid from the polymer due to anhydride formation. To be commercially attractive, JOneS glue, C. without the attendant problems mentioned above.

It would be highly desirable to provide improved properties such as polymers.

Efforts have been made to introduce effective phenolic functionality into polymer coating vehicles in order to improve the curing properties or properties of the coatings produced. However, coatings produced by prior art techniques typically
Has drawbacks or difficulties in manufacturing.

U.S. Patent No. 4,446,302, Re-registered Patent No. 32,136, and U.S. Patent No. 4,416,965, all by 5andhu et al., repeat units derived from diols and diacids. , as well as repeating units derived from p-hydroxybenzoic acid. These polyesters are used in electrographic developer compositions.

The polymers disclosed in 5andhu et al. have several drawbacks. The repeat units derived from PI (BA) are blocks of two or more PHBA units. The polymer also has a high molecular weight as evidenced by a high internal viscosity of about 0.3 to 0.7. (MW50.00
0-200,000). Finally, the polymer is made from p-acetoxybenzoic acid and is therefore carboxy-terminated.

) 1 einrich U.S. Pat. No. 2.979.473 is made from a polyacid, a polyol and a modifier,
3 containing 0 to 100 mol% 2,4-dimethylbenzoic acid
It relates to alkyds containing 0 to 70 mol % of monocarboxy aromatic acids.

Helnrich, US Pat. No. 2,993,873, relates to alkyd resins that are modified by reaction with hydroxybenzoic acid and cured at ambient conditions or by baking. No crosslinking agent is added in either case. Rather, curing progresses due to unsaturated sites in the alkyd resin,
The coatings produced thereby do not have the advantages achieved by the incorporation of crosslinkers.

U.S. Patent No. 4.543.952 by Sha 1aby
No. 1, No. 1, No. 1, No. 1, No. 1, No. 2003, P) discloses copolymers formed by polycondensation of IBA, an acid anhydride, and a diol. However, as in the Andhu et al and Helnrich patents, the polymers produced are not PHBA end-capped, but rather have a random structure.

U.S. Pat. No. 3,836,491 and B to Taft
U.S. Patent No. 4.343.839, U.S. Patent No. 4,374.181, U.S. Patent No. 4.365 to legen
．． No. 039 and U.S. Pat. No. 4.374.167,
Compositions are disclosed that include a fer/fer terminated polyester component that can be cured at room temperature with tertiary amino acids and a polyisocyanate curing agent. These systems are unstable at room temperature and must be stored in two separate packages that are mixed immediately before application. Taft discloses a number of uncapped prepolymer components that can be reacted with carboxyl phenol to provide a wide variety of capped hydroxy-containing polymers for subsequent reactions.

However, Taft and Blegen have shown that mixing the polymer and polyisocyanate in the presence of a tertiary amino (basic catalyst) and subsequent reaction rapidly (
We refer to a two-pack polyurethane system that results in a composition that hardens (within a few minutes).

Coatings produced by this method do not exhibit the improved properties achieved by baking and curing the coating. Furthermore, to avoid direct esterification of hydroxybenzoic acid, Taft relies on the difficult transesterification of the methyl ester of hydroxybenzoic acid. Therefore, to provide acceptable conversion, a significant excess (approximately 2 times) of methyl salicylate, i.e., the methyl ester of hydroxybenzoic acid, must be used, thereby removing the excess methyl salicylate. An additional vacuum stripping procedure by heating to 350° F. at 0.05 mm Hg is required to achieve this. Furthermore, approximately 25% of methyl salicylate cannot be removed.

Accordingly, this makes the products and methods disclosed in Taft commercially undesirable and uncompetitive.

Linden U.S. Pat. No. 4.331.782, “
According to the patent, hydroxybenzoic acid is pre-reacted with an epoxy compound such as Cardura E (glycidyl ester of neopentadecanoic acid) in a first step to form a polymer as described below. Manufacture adducts.

L:H2UU-tsH+s Step 1 protects the carbokylene group of PHBA, prevents the deactivated carbokylation, and further removes the reactive hydrocyanyl moiety to facilitate the next reaction with other components. is formed on top of the appendage. In the second step, the adduct is reacted with neopentyl glycol, adipic acid and isophthalic acid to produce a phenol-functional polyester.

Linden suggests that direct reaction of hydroxybenzoic acid and polyol for the synthesis of polyesters is impractical as degradation of the hydroxybenzoic acid predominates. This patent discloses that further advantages achieved include the ability to synthesize phenolic functional polymers without exposing hydroxybenzoic acid to conditions that tend to decarboxylate it.

Linden further discloses a method for producing polyester polymers that are substantially free of reactive aliphatic hydroxyl groups to increase the pot life of the coating compositions produced. However, reactive aliphatic hydroxyl groups are desirable, even essential, in some cases.

U.S. Patent No. 4.267, 2 to TiankaChan et al.
No. 39 and No. 4,298.658 disclose alkyd resins containing free hydroxyl groups modified by reaction with PHBA. The modified alkyd is cured by a steam curing process using di- or polyisocyanates at room temperature in the presence of amino vapors. These are also two-package systems that must be stored separately. Coatings produced by this method have limited properties because they do not contain amino crosslinkers and are baked at elevated temperatures.

Japanese Patent Nos. 52-73929, 52-81342 and 53-42338 relate to powder coating compositions comprising amino resins and polyester resins having phenolic hydroxyl groups and having a softening temperature of 40°C to 150°C. Japanese Patent Nos. 52-81341 and 53-423
No. 41 is similar, but introduces a double bond into the polyester structure to reduce the amount of crosslinking required by the amino crosslinked resin, and to reduce the amount of amino resin required, Enables the second mode (oxidizing). However, these patents all relate to powder coatings that require the resin system to be solid at the conditions of application. Therefore, they must have a high softening temperature, ie the glass transition temperature of the polyester resin must be high. In addition, powder coatings require special application techniques and are widely used in:'! Not used. Furthermore - for boat fishing techniques a liquid system is required.

The present invention relates to liquid polymer and liquid polyol compositions for improved coatings with improved properties. These coatings simultaneously provide high hardness and high impact resistance, good weather resistance, good corrosion resistance and hydrolytic stability, solvent resistance, adhesion, low staining and low impurity levels. These properties are L, C
, obtained without the introduction of polymers or mesogenic groups, and therefore B.

C. Many disadvantages of primers can be avoided.

For example, the present invention provides polymers without expensive mesogenic groups, saving costs. Second, the present invention provides an improved, less expensive, and easier synthetic method that results in substantially improved polymer coloration.

This is important from a commercial point of view, as it allows the production of light and white coatings, which are important marketing factors. Furthermore, according to the improved synthetic method,
L.

Another drawback of C polyester-based polymers, namely the decomposition of the polyester part of the polymer, in which phthalic anhydride is formed in large quantities, is avoided. This phthalic anhydride beam, C,
It provides an easily volatilized material that remains in the polymer mixture and can have a detrimental effect on the application and curing of the coating.

Additionally, unlike conventional two-package polyurethane coating systems in which the individual packages are stored separately and the two packages are premixed immediately prior to application, the liquid polymer or polyol compositions of the present invention provide a completely mixed, almost unlimited It can be applied as a homogeneous mixture that exhibits a shelf life and then cures to produce a crosslinked polymer with excellent properties.

The invention further relates to a process for producing hydroxybenzoic acid capped polymers or polyols, which avoids extensive decarboxylation of the hydroxybenzoic acid starting material.

These and other purposes; in addition to the solid, crosslinked polymer compositions produced by curing the polymers of the present invention, liquid polymer compositions containing a non-liquid crystalline ester phenol capped polymer and an amino crosslinker; This is achieved by providing

Liquid polyol compositions comprising a non-liquid crystalline ester phenol-capped polyhydric alcohol and an amino crosslinker are also provided. The properties of conventional films or surface coatings produced by curing conventional films or liquid film-forming or coating formulations can be modified by adding ester-phenol-capped polymers or ester-phenol-capped polyhydric compounds in the film-forming or coating formulation before curing. A method of improvement is provided by replacing all or one of the conventional aliphatic hydroxy- or epoxy-functional polymers or polyhydric alcohols, respectively, with alcohols.

Hydroxybenzoic acid-capped polymers or polyhydric alcohols are prepared by direct esterification of aliphatic hydroxy-functional polymers or polyhydric alcohols with hydroxybenzoic acid at reaction temperatures below 200°C. In another embodiment, the hydroxybenzoate polymer is
It is prepared by reacting a 1 molar excess of aliphatic hydroxy-functional polymer or polyhydric alcohol with hydroxybenzoic acid at a reaction temperature below 200° C. to partially esterify the polymer or polyhydric alcohol. The reaction mixture is then reacted with a polybasic acid or acid derivative at below 200° C. until the desired level of conversion of carboxy groups to esters is achieved.

Another embodiment of the invention is to charge all reactants (polyalcoholic acid, hydroxybenzoic acid) at the same time,
This is carried out by carrying out esterification of the reaction mixture at temperatures below 200° C. until the necessary conversion of carboxyl groups into ester groups is achieved.

In yet another aspect of the invention, the improved liquid polymer and polyol compositions are formed into coating formulations by addition of solvents, catalysts, and additives.

The liquid polymer and polyol compositions of the present invention are useful in surface coatings, films, adhesives, and any other applications requiring similar properties.

In accordance with the present invention, there are provided improved liquid polymer vehicles or liquid polyol vehicles for coating compositions that result in coated polymers with improved properties, and methods for their preparation. The improved liquid polymer vehicle may include (a) an ester phenol capped polymer (oligomer), and (b) an amino crosslinker, and optionally (C) an organic solvent. The improved liquid polyol vehicle comprises (d) an ester phenolic medium molecular weight polyol, such as a polyhydric alcohol having from 12 to 40 carbon atoms, and (b) an amino crosslinker, and optionally (C) an organic solvent. Good too.

The improved liquid polymer vehicle or liquid polyol vehicle does not contain liquid crystal polymers or mesogenic groups. The liquid vehicle is made into a coating formulation by adding conventional solvents, pigments and additives used in coating compositions such as flow control agents and stabilizers. The coating formulation can be applied by conventional methods such as coating, spraying, roller coating, or dipping.
applied to the base material. Thereafter, the coated substrate is baked and at the same time the solvent is evaporated and the mixture (a) or (
The final film is formed by crosslinking d) with an amino crosslinking resin. The films of the invention have improved properties compared to films formed by similar (in molecular weight, functionality, etc.) polymeric vehicles without ester phenolic groups, such as higher hardness and higher It is characterized by simultaneously having impact resistance, good weather resistance, good corrosion resistance and hydrolytic stability, solvent resistance, low coloration and low impurity levels, and good adhesion.

To describe the present invention, the following terms are defined.

"Liquid polymer composition" means a polymer composition that is liquid at room temperature.

“Hydroxy liquid crystal polymer” is described by Dimian, A.
F.

Jones, F. N., J. Polym.
Mater, Sc3 Eng, 1987.56 X-ray analysis technique and/or polarization microscopy technique (op.
tical polarizing m1crosco
refers to a polymer characterized by the absence of detectable amounts of liquid crystals, as measured by pytechniques).

“Derived from” (e.g. “1 derived from Kilimer”
Polyvalent groups" or "multivalent groups derived from polymers" can be obtained by (1) removing at least one hydroxy group from either a polyester, alkyd or acrylic polymer, or (2) removing from an epoxide polymer. at least 1
means a monovalent or polyvalent group obtained by changing the configuration of epoxy groups (for example, when the polymer is a hydroxy-terminated polyester with two or more aliphatic hydroxy groups, such A monovalent group derived from a polymer is a monovalent group produced by removing one hydroxy group, and a polyvalent group derived from such a polymer is a monovalent group generated by removing one hydroxy group. A divalent (multivalent) group produced by removing more hydroxy groups; if the polymer is an epoxide having two or more epoxy groups, it is derived from such an epoxide polymer. A monovalent group refers to a primary monovalent group generated by changing the arrangement of one epoxy group to generate a β-hydroxy substituent site, and a polyvalent group refers to a β-hydroxy substituent group. is a primary divalent (polyvalent) group produced by changing the arrangement of two or more epoxy groups in an epoxy group to produce a hydroxy substituent; this term refers to a monovalent or It does not imply that the multivalent group must be prepared from a polymer precursor.

The term "hydrocarbylene" refers to a divalent hydrocarbon radical.

The term “oxygen-hydro-rubylene” refers to the oxygen-containing group,
For example, it means a divalent hydrocarbon group having a carbonyl group, an ester group, a 21-thyl group, a hydroxy group, or a phenol group.

The term “acid derivative”; well, a chemical reaction that is substantially the same as that of an acid;
For example, it refers to derivatives of acids capable of undergoing esterification (such derivatives include, but are not limited to, acid halides, esters and acid anhydrides).
.

The non-liquid crystalline ester phenol-capped polymer of component (a) of the improved liquid polymer vehicle has the following formula: 20
represents a polyvalent group having a number average molecular weight of 0 to about 10,000, R1 represents a direct bond, a C1 to C20 hydrocarbylene group, or a C1 to C20 oxyhydrocarbylene group; (R' representing a lene group preferably represents a direct bond), R2 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carbon atom number 1 to 4
R2 representing an alkoxycarbonyl group preferably represents a hydrogen atom), and n represents an integer of 2 to 10 (preferably n represents an integer of 2 to G, more preferably an integer of 2 to 4). and most preferably represents 2.)) The group R is a divalent or polyvalent hydrocarbon (aromatic, aliphatic or mixtures thereof) which can optionally have ester, epoxy or ether bonds. represents the group of The number average molecular weight ranges from about 200 to 10,000, preferably from about 200 to 6
The range is 000. In one embodiment, R is
The ester funinol cap 7' holJmer can be derived from di- or polyhydroxy oligomer precursors that can be used to synthesize, especially by esterification reactions. Preferred examples of these oligomer precursors are di(
Poly) hydroxyl esters, alkyds or acrylics. In other embodiments, R is specifically, by reaction with the carboxyl group of the capping compound to produce a hydroxy-substituted ester phenol-capped polymer.
Ester may be derived from polyepoxides that may be used to synthesize phenol-capped polymers. Otherwise, precursors having functional groups of the structural formula below can be used to make liquid polymer vehicles.

Imide group Amide group Urethane group (in the above formula, 0 represents a hydrogen atom or an alkyl group) Preferably, a component of the improved liquid polymer vehicle (
The non-liquid crystal ester phenol cap polymer a) is represented by the following formula.

(In the formula, R3 represents a divalent group having a number average molecular weight of about 200 to 10,000 derived from a hydroxy-terminated polyester. The polyester preferably contains one or more polyhydric alcohols and one type or more polybases or derivatives thereof.) In another embodiment of the present invention, the main chain group R is
It can be derived from simple molecules of medium molecular weight, for example polyhydric alcohols of 12 to 40 carbon atoms capped with ester phenols. In that case, the liquid polymer composition is more precisely defined as a liquid polyol composition. However, for simplicity,
In the specification, the terms "liquid polymer vehicle,""liquid polymer composition," and "liquid polyol composition" are used interchangeably, and preferred embodiments of the liquid polymer vehicle (liquid polyol composition) are used interchangeably in the specification. The same applies to the composition. Preferably, the liquid polyol composition is represented by the formula:

(In the formula, R4 represents a divalent group derived from a diol having 12 to 40 carbon atoms.) The following general formula represents an ester phenol cap group.

(In the formula, Rl represents a bond of a phenol group to an ester group, and represents a direct bond, an oxygen atom, or a divalent and aliphatic or aromatic group which may optionally contain a carbonyl group or a phenol group.) R When ' represents a divalent group, it may contain 1 to 20, preferably 1 to 11, and more preferably 1 to 7 carbon atoms. R2 represents the above meaning.

Examples of compounds from which ester phenol cap groups are derived are shown below.

When hydroxyphenylacetic acid hydroxyphenylpropionic acid hydroxycarboxybenzophenone R' is directly attached to the base, the above formula is limited to hydroxybenzoic acid which can be 0-1 p- or m-. A preferred fruit is p-hydroxybenzoic acid (PH
BA).

Component (a) of the improved liquid polymer vehicle, the non-liquid crystal ester phenol capped polymer (I), may be used as a substantially pure compound or as a mixture with other compounds. In one embodiment, (I)
are prepared by combining mixtures made from different starting materials and can be used as mixtures of similar but different compounds. In a preferred embodiment, (
T) is used as a mixture of the starting materials used in the production and the intermediate compounds in the production. In this embodiment, the ester phenol-capped polymer is prepared in a sequential step from a high molecular weight di(poly)ol (polyester, alkyd or acrylic) or a high molecular weight di(poly)epoxide precursor.

The precursor is reacted with the cap group in successive steps. In the first step, a monosubstituted derivative (I[
) is manufactured. In the next step, a derivative having ester phenol groups on both sides of the polymer is produced.

It is also possible, but not essential, for the purposes of the present invention to react other parts of the polymer. The sequential steps are shown below.

(wherein: R represents a polyvalent group derived from a polymer having at least two aliphatic hydroxy groups or epoxy functional groups and has a number average molecular weight of about 200 to 10,000; R' is a direct bond, a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms (preferably R1 represents a direct bond), R2 is a hydrogen atom, a hydroxyl group, a halogen atom,
C1-C4 alkyl group, C1-C4 alkoxy group, or C1-4 alkoxycarbonyl group (preferably R2 represents a hydrogen atom); represents a monovalent group having a number average molecular weight of about 200 to 10,000 derived from a polymer having an aliphatic hydroxyl group or an epoxy functional group, n represents an integer from 2 to 10, preferably n represents an integer from 2 to 10; It represents an integer of 6, more preferably 2 to 4, most preferably 2. ) One embodiment; in which the oligomer precursor that can be used to synthesize the ester phenol cap polymer is a low molecular weight polyester diol. This can be produced by a condensation reaction between a di- or polyol and a di- or polyacid. The polyol usually contains 2 to about 8, preferably 2
~6 carbon atoms and 2 to 6, preferably 2 to 4 hydroxyl groups. Examples of preferred polyols are one or more of the following polyols: neobentyl glycol, ethylene glycol, propylene glyconopebutanedionobenhexamethylene diol, 1.2
-Cyclohexane dimetatool, 1゜3-cyclohexane dimetatool, 1.4-cyclohexane dimetatool, trimethylolpropane, pentaerythritone vediethylene glycol, triethylene glycol, tetraethylene glycol, dibropylene glycone polybrobylene Glyconobehexylene Glyconope 2-
Methyl-2-ethyl-1,3-7'lopandionobe 2
-Ethyl-1,3-hexanediol, 1,5-bentanediol, thiodiglyconobe 1. 3-propanedionobe 1,3-butanediol, 2.3-butanediol, 1,4-butanediolbe 2,2,4-trimethyl-1,3-bentanediol, 1,2-cyclohexanediol , 1°3-cyclohexanediol,
1.4-Cyclohedoxanediol, glyceronobe trimethylolpropane, trimethylolethane<1.
2. To 4-butanetriots1. 2. 6-hexanetrione/benpentaerythritol, tripentaerythritonohemannitol, sorbitol, methyl glycosides, and similar compounds apparent to those skilled in the art, as well as mixtures thereof. The polyacids have about 2 to 34 carbon atoms in the aliphatic or aromatic portion and at least 2, preferably no more than 4, carboxyl groups which may be present in the anhydride form. The polyacid is preferably one or more of the following acids: phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, schifhexanedicarboxylic acid, trimellitic acid. acid anhydrides, azelaic acid, sebacic acid, dimer acid, pyromellitic dianhydride, substituted maleic and fumaric acids, such as citraconic acid, chloromaleic acid, mesaconic acid, and substituted succinic acids,
For example aconitic acid and itaconic acid. It is possible to use mixtures of polyols or polyacids, or both.

In the preferred aS type, polyester diol (
II) is reacted with PHBA in a stepwise manner as described below to produce an ester phenol compound polymer.

I rV ■ In the first step, PHBA is reacted with one end of a polyester diol to produce a polymer with one aliphatic hydroxy group and one ester phenol group (rV). In the second step, the second PHB
A is reacted with ■ to produce an ester phenol cap polymer (V). The distribution of reaction products is controlled by the amount used in PHB. With stoichiometric amounts of PHBA, the reaction produces almost exclusively V, and with less PHBA, the reaction is stopped early to give a mixture of 1, 2, and V. This mixture also constitutes a preferred embodiment of the invention. When using low amounts of PHBA), ■ becomes predominant, and a small amount of ■ and a very small amount of ■ can be produced. With larger amounts of PHBA,
■ increases, ■ decreases, and ■ begins to increase. When a larger amount of PHBA is used, ■ and ■ become the main components, and a small amount of ■ is present. Furthermore, when using a very large amount of P HB A, ■ is produced exclusively.

In another embodiment, the diol can be converted to hardness by using a large amount of PHBA, and the reaction can be carried out such that ■ is predominant, with small amounts of ■ and ■ of the solder. Then, to produce one of the preferred types,
This component can be combined with additional unreacted starting material (1). The resulting formulation is dominated by ■ and ■;
is present in very small quantities.

In other embodiments, the di- or polyhydroxy oligomer precursor used in the synthesis of the ester phenol-capped polymer is an alkyd resin. Alkyd resins are oil-modified polyester resins, more broadly derived from dihydric or polyhydric alcohols, di- or polybasic acids or acid derivatives, and fats, fats or oils or fats that act as modifiers. It is a reaction product with carboxylic acid. Such modifiers are typically drying oils. The dihydric or polyhydric alcohol used in the first step is preferably an aliphatic alcohol; suitable alcohols include glyconobe 1.2- or 1,3-propylene glyconobe, butanediobehexanediol, neopentyl Includes glycols, glycerol, trimethylolethane, trimethylolpropane and pentaerythritol.

In particular to provide the desired content of hydroxy groups,
It is also possible to use mixtures of alcohols. When pentaerythritol is used alone as the alcohol component, it tends to crosslink between the hydroxy groups, forming a more brittle coating.

The dibasic or polybasic acid or corresponding anhydride is selected from a variety of aliphatic and aromatic carboxylic acids. Suitable acids and acid anhydrides include, for example, succinic acid, adipic acid, phthalic anhydride, isophthalic acid, trimellitic anhydride and bis3.3'.

4.4'-benzophenonetetracarboxylic acid anhydride is included. Mixtures of these acids and anhydrides can also be used to obtain certain properties.

Suitable drying oils or fatty acids for use are C 12 -C 22 saturated or unsaturated fatty acids or the corresponding triglycerides, ie those contained in the corresponding fats or oils, such as animal or vegetable fats or oils. Suitable fats and oils include tall oil, castor oil, coconut oil, one part lard, one part linseed oil, one part coconut oil, bean oil, rapeseed oil, soybean oil and beef tallow. Such fats and oils include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, valmitic acid and stearic acid, as well as unsaturated fatty acids such as oleic acid, eracic acid, ricyl acid, linoleic acid. and a mixture of triglycerides of lylic acid. Chemically, these fats and oils are usually mixtures of two or more of this group.

As shown above, the polymer precursor group R12 is a divalent group R
The number average molecular weight of the trivalent or monovalent group R5 is approximately 20
It ranges from 0 to about 10,000.

For certain applications, where more flexible coatings are required, such as coil coatings, the molecular weight of these groups is preferably on the higher end of this range, at least about 3,000, and more preferably about 3,000 to about 6,000. In most other applications where a coating with higher hardness is desired, the molecular weight of these groups will be on the lower end of the above range, less than about 3,000, more preferably from about 200 to about 1.500. is within the range of

When the oligomer precursor from which the main chain group R is derived is a polyester or alkyd resin, the number average molecular weight is preferably in the above range of 200 to 6.000.

In yet another embodiment, the di- or polyhydroxy oligomer precursor used to synthesize the ester phenol-capped polymer is a 771J copolymer resin. The acrylic copolymer resin has at least one
hydroxy-substituted alkyl acrylates (methacrylates) and at least one non-hydroxy-substituted alkyl acrylate (methacrylate). Hydroxy-substituted alkyl acrylates (methacrylates) which can be used as monomers contain moieties selected from the group consisting of acrylic or methacrylic acid and esters of aliphatic glycols: 2-hydroxyethyl acrylate, 3-chloro-2-hydroxy Propyl acrylate; 1-hydroxy-2-acryloquine propane, 2-hydroxypropyl acrylate, 3-
Hydroxypropyl acrylate; 2.3-dihydroxypropyl acrylate; 3-hydroxybutyl acrylate; 2-hydroxybutyl acrylate; 4-hydroxybutyl acrylate; diethylene glycol acrylate; 5-hydroxypentyl acrylate; 6-
Hydroxyhexyl acrylate; Triethylene glycol acrylate; 7-hydroxybutyl acrylate; 1-hydroxy-2-methacryloxypropane; 2
-1)'Loquinpropyl methacrylate); 2,3-dihydroxypropyl acrylate; 2-hydroxybutyl methacrylate; 3-hydroxybutyl methacrylate; 2-hydroxyethyl methacrylate; 4-hydroxybutyl methacrylate; 3゜4-dihydroxybutyl methacrylate ; 5-hydroxypentyl methacrylate; and 7-hydroxyhebutyl methacrylate. Those skilled in the art will appreciate that many different hydroxy-substituted alkyl acrylates (methacrylates) may be used, including those listed above, and that preferred hydroxy-functional monomers for use in the resins of the present invention may contain a total of 5 to
It will be understood that they are hydroxy-substituted alkyl acrylates (methacrylates) having 7 carbon atoms, ie esters of dihydric alcohols having 2 to 3 carbon atoms and acrylic acid or methacrylic acid. Examples of particularly suitable hydroxy-substituted alkyl acrylate (methacrylate) monomers are 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxypropyl acrylate.

Non-hydroxy substituted alkyl acrylates used
Among the (methacrylate) monomers, alkyl acrylates (methacrylates) (meaning esters of acrylic acid or methacrylic acid as mentioned above) are preferred.

Preferred non-hydroxy unsaturated monomers have 1 carbon atom
to 12 monohydric alcohols and acrylic acid or methacrylic acid, such as methyl methacrylate,
These include hexyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and glycidyl methacrylate. Examples of particularly suitable monomers are butyl acrylate, butyl methacrylate and methyl methacrylate.

Additionally, the acrylic copolymer resins of the present invention may contain other monomers in the composition, such as acrylic acid and methacrylic acid.
Monovinyl aromatic hydrocarbons having 8 to 12 carbon atoms (
For example, styrene, alpha-methylstyrene, vinyltoluene, tert-butylstyrene, chlorostyrene, etc.), vinyl chloride, vinylidene chloride, acrylonitrile, and methacrylonitrile).

The acrylic copolymer preferably has a molecular weight of about 1000 to 6000
, more preferably a number average molecular weight of about 2,000 to 5,000.

In another embodiment, epoxy resins are used in the synthesis of ester phenol capped polymers. The epoxy resin of the invention is characterized by the presence of two or more types of three-membered cyclic ether groups (epoxy groups or 1°2-epoxides) and is understood as an anhydride type of 1,2-diol. Vine. The synthesis of ester phenol-capped polymers from epoxy resins is different from the simple esterification of polyols discussed above and is based on the following reaction.

Compound (1) has four or more functional groups per molecule (depending on the structure of R'). The most widely used epoxy resins are diglycidyl ethers to bisphenols. Other commercially produced gepoxy resins are hydantoin-based (e.g. C1b
a Geigy EpoxyResin 0163)
, and alicyclic type (Union Carbide). Multi-epoxy functionalities include epoxy phenolic novolaks (DOW ("chemical Company's DEN431, DEN 438.
This is recognized as PI (the reaction between BA and epoxy resin is
Compared to di(poly)ol esterification, it proceeds under milder conditions (lower temperature, shorter time), and PHB
The risk of decomposition of A is reduced. However, this chemistry only foils for bis- or poly-epoxy resins or compounds and is therefore limited as to the possible structures of the ester phenol-capped polymer relative to the corresponding epoxy resin.

The amino crosslinkers used according to the invention are well known commercial products. They are organic compounds represented by the general structural formula below.

(In the formula, u>2;R'=H, or an alkyl group having 1 to 4 carbon atoms In the above formula, Q and R5 represent the same meanings as defined above, and M is the following melamine, benzoguanamine, Represents the residue of urea or glycoluril.

The amino crosslinkable resin is, for example, American Cya
nam+d.

It is produced by the reaction of a di(poly)amide (amino) compound, formaldehyde, and optionally a lower alcohol.

Currently commercially produced amino crosslinked resins are based on the following compounds:

Melamine Benzoguanamine D Urea Glycoluril In the present invention, the ratio of effective crosslinking groups, ie methylol (alkoxymethyl) groups of the amino crosslinker, to phenolic groups of the ester phenol capped polymer or polyhydric alcohol is preferably about 1.0: 1.0-15.0
:1.0, more preferably about 1, o:1.0-5.0:
1.0, most preferably about 1.5:10 to 4.0
:1.0.

The amount of amino crosslinker effective to cure the crosslinkable binder is generally about 30% by weight, based on the total amount of amino crosslinker, ester phenol capped polymer, and any crosslinkable polymer components of the composition. The range is from about 50 parts by weight, more preferably from about 10 to about 40 parts by weight. Typically, the amount of crosslinking agent required to cure the composition is inversely proportional to the number average molecular weight of the ester phenol capped polymer composition. Relatively low number average molecular weight, e.g. about 2
00 to about 3,000, an amount of crosslinking agent at the higher end of the range is required, while a higher number average molecular weight, e.g. 3,000 to about 10,000
Lower amounts of crosslinker are required to properly cure ester phenol-capped polymers having

Examples of suitable amino-bridged fats for liquid vehicles are shown below.

N (CHJR) 2 In the formula, R represents the following meaning R = CH5 (Cymel"300.301.303)
:R=CH3,CJs(CymelT″1116);R
=CL, CJa ([:ymelTXn3o, 11
33) :R=CJ* (CymelTX1156)
; or R=CH=, H(CymelTX37
0.373.380.385) A preferred melamine is hexamethoxymethylmelamine.

In the benzoquanamine base resin formula, R=CL, C2H5 (Cymel"1123)
In the formula, R represents the following meaning.

R=CH3,H(Beetle 60. Beetle
65); or R=mouth Js (Beetle 8
0).

Glycoluril based resin In the formula, R represents the following meaning.

R=CH3,CJs(CymelTl″1171);
or R=CJs (Cymel” 1170).

The liquid polymer vehicle can also include pigments. Preferably, the pigment is in a ratio of about 0.5:1.0 to 2.0:1.0, more preferably 0.5:1.0 to 2.0:1.0, based on the sum of the ester phenol cap polymer and amino crosslinker in the vehicle.
Present in a weight ratio ranging from 8:1.0 to 1.1:1.0.

The present invention provides an improved polymer vehicle for providing films with improved properties, such as high hardness and high impact values at the same time. A high shock value reflects high flexibility, and high flexibility is due to the T of component (a).
Depends on g value. To impart high flexibility, the Tg of component (a) should be below about 40°C, preferably between -40°C and 40°C, more preferably between -30°C and 35°C.
C, and most preferably -20C to 30C. Component (a) is a mixture and the Tg of the mixture is measured by conventional means or calculated from the formula below.

Tg TgI TgIf TgIII
In the formula, WLWn and wm represent the parts by weight of the components of Formula 1, (1) and (2), and TgI, Tgn, and TgIII represent the corresponding glass transition temperatures.

Conventional coating systems require acidic catalysts to cure with amino crosslinking resins.

However, in the present invention an alternative curing route can be used and surprisingly no acid catalyst is required. In fact, no catalyst is required). The desired crosslinking reaction is obtained simply by heating the liquid polymer vehicle. Time and temperature depend on the particular reaction system, and conditions are generally similar to those used with acid catalysts. Another surprising property of the present invention is the use of base catalysts in the present invention. It has been found advantageous that a suitable base is an alkali metal or alkaline earth metal salt of a weak acid, such as potassium neodecanoate.The catalyst can be used in the same amount as the strong acid catalyst. The method for burning is also the same.

Another object of the invention involves the production of ester phenol capped oligomers. There are several problems with the conventional introduction methods discussed in the literature. It has been shown many times in the prior art that in the direct esterification of polyols with hydroxybenzoic acid, large amounts of hydroxybenzoic acid are decarboxylated and phenol and carbon dioxide are formed. In fact, Linden U.S. Pat. No. 4,331,782 teaches that the direct reaction of hydroxybenzoic acid with a polyol for the synthesis of polyesters is
This suggests that it is impractical due to the decomposition of hydroxybenzoic acid. Therefore, large amounts of decarboxylation destroy large amounts of expensive hydroxybenzoic acid, making the process impractical. Other problems with direct esterification also represent important drawbacks of the process. Jones is
Filed on March 28, 1988, October 1, 1988
In European Patent Application No. 287233, published on the 9th, the direct esterification of oligomers (including phthalic acid, adipic acid and neopentyl glycol) with PHBA using a p-TSA catalyst and high-boiling aromatic solvents is suggested. are doing. However, this process is characterized by the fact that very strongly colored products are obtained and large amounts of oligomer decompose into phthalic anhydride. It is therefore very difficult to use this product for the production of light or white paints. The presence of large amounts of phthalic anhydride also makes it difficult to use in some methods for coating applications. Furthermore, there is also the problem that the amount of volatile matter evaporated increases. In the process of the invention, it has been found that the choice of process makes it possible to overcome all of these problems and achieve direct esterification.

In the present invention, two methods are used to minimize or eliminate the above problems, such as (1) precise adjustment of the reaction conditions, i.e., minimizing exposure of the hydroxybenzoic acid to high temperatures; and (2) the use of hydroxybenzoic acid containing no or very small amounts of basic impurities (separately or in combination).

In one embodiment, a two-step reaction is used. In the first step, hydroxybenzoic acid is
A molar excess of a C2-C8 polyhydric alcohol, such as neopentyl glycol, is mixed. Preferably,
The ratio of C2-C8 polyhydric alcohol to hydroxybenzoic acid ranges from about 1.1 to 10:1. A suitable solvent and optional catalyst are added and the solution is stirred and heated to 140-200<0>C. The excess amount of neopentyl glycol subsequently reacts and helps the reaction to occur due to the mass effect effect, resulting in faster reaction rates using lower reaction temperatures. After most of the reaction water has been removed, other monomers, such as polybasic acids or derivatives thereof, are added and the second stage of the reaction is carried out at a temperature of 140-200<0>C.

This technique maintains temperatures below 200°C and minimizes decarboxylation of hydroxybenzoic acid. The reaction may be completed by increasing the reaction temperature, preferably about 200-230<0>C, to esterify the remaining reactants.

In another embodiment, a one-step reaction is used.

Combine all of the reactants, catalyst (if desired) and solvent;
Heat to a temperature of 140-200°C. At this level it is important to maintain the temperature such that at least about 5%, preferably 70%, and more preferably at least about 80% esterification reaction occurs. The water of reaction is used to monitor the progress of the reaction. At a suitable time, the temperature should be increased to e.g.
Raise the temperature to 30°C to complete the reaction.

In a third embodiment, aliphatic hydroxy-functional polymers can be prepared by conventional methods in the absence of hydroxybenzoic acid. This polymer or a polyhydric alcohol having 40 carbon atoms is then added to the hydroxybenzoic acid at a temperature of 140 to 200°C to reduce the amount of at least 5%, preferably 70%, more preferably less than 80%. The reaction can be carried out until a conversion of .

The temperature is then raised to about 230°C to complete the reaction. This method of introduction can be advantageous in some cases for the synthesis of ester phenol-capped polymers or polyols to obtain narrow molecular weight distributions.

Generally, 5% or more by weight of aliphatic hydroxy-functional polymers or polyhydric alcohols having from 12 to 40 carbon atoms are esterified to produce hydroxybenzoic acid-capped polymers or polyols. Additionally, aliphatic hydroxy-functional polymers or C 12 to C 40
The amount of hydroxybenzoic acid used to esterify the polyhydric alcohol of 1.
The range is about 0.05 to 1.25 equivalents per 0 equivalents, preferably 0.25 to 1.0 equivalents of hydroxybenzoic acid per 1.0 equivalents of polymer or alcohol.

The reaction can be carried out in the presence or absence of a catalyst.

Although the reaction can be allowed to proceed to completion without a catalyst to produce good quality ester phenol substrate oligomers, the addition of a suitable catalyst is advantageous in accelerating the reaction. Suitable catalysts for the reaction include a variety of metals of groups I to II, known as catalysts for esterification and transesterification, such as 2n, Sn, AI, Mn.
, and Ti) oxides, salts, and alcoholades. Other catalysts include B2O3, H3BO3, 5b20
3, metalloid compounds such as As20i and the like. The catalysts used can be weak acids, such as phosphorous acid, phosphoric acid, hypophosphorous acid, or strong acid catalysts, such as p-)luenesulfonic acid and methanesulfonic acid. These catalysts may be used in amounts ranging from about 0.01% to about 2.0% by weight.

In some cases, no solvent is required during the synthesis of the ester phenol-capped liquid polymer or polyol. In other cases, one or more solvents may be used to dissolve the reactants. If solvents are used, they should be inert during the esterification reaction. Hydrocarbon solvents are preferred, and aromatic hydrocarbon solvents are most preferred.

Distillation of water is used to monitor the reaction to determine the appropriate time to complete the reaction, which can vary from about 4 hours to about 30 hours, preferably from 6 to 20 hours.

The relative amounts of compounds (1) and (2) and (2) are determined by stoichiometry or by the amount of hydroxybenzoic acid.

In the present invention, it has been discovered that decarboxylation of hydroxybenzoic acid can be minimized by minimizing or eliminating certain impurities that catalyze decarboxylation. Such impurities are basic compounds, especially alkali metal or alkaline earth metal salts of weak acids.

The most common examples of these basic impurities are potassium salts and/or potassium phenolates of PHBA, which are often present as impurities in commercially available PHBA.

The presence of potassium salts is an intermediate in the production of PHBA, p
- Occurs due to incomplete neutralization of potassium hydroxybenzoate or potassium phenoxide. Other basic compounds, such as those that react with P)(BA to yield the PHBA anion) also promote depotent levoxylation.To this end, very low amounts of base are used to avoid depot levoxylation It has been found that high purity PHBA should be used, for example containing potassium salts. Another method to avoid decarboxylation is to neutralize basic impurities with the acid used in the catalyst that catalyzes the esterification process.

In the process, care should be taken to avoid an excess of acidic catalyst, as excess acidic catalyst tends to be detrimental to the production of baked films.

Preferably, the esterification reaction mixture is 0.2% or less,
Most preferably it contains less than 0.0001% of basic impurities, especially alkali metal or alkaline earth metal salts of weak acids, such as PHBA or the potassium salt of potassium phenolate.

The present invention relates to a novel coating vehicle formed by combining component (a), an amino crosslinker, and (optionally) a solvent. Application of the coating formulation is carried out by conventional methods such as spraying, roller coating, dip coating, etc., and the applied system is then cured by baking. The same or different solvent optionally used during the reaction of the ester phenol-capped polymer or polyol vehicle to dissolve the reactants is added during the formulation of the coating composition to achieve a viscosity of typically about 10 centipoise to 10 poise. One or more solvents may be used which may adjust the viscosity to provide the formulation. Often a single solvent is used to dissolve the system. However, it is often desirable to use solvent mixtures in order to obtain the best solubility, and in particular combinations of aromatic and oxygenated solvents are particularly preferred. Suitable aromatic solvents include toluene, xylene, ethylbenzene, tetralin, naphthalene, and narrow cut aromatic solvents including L'L13 aromatics having 8 carbon atoms, e.g. Snxxon Company II, S, A
, from Aromatic
15Q and Aromatic 200. Oxygenated solvents should not be so polar that they become incompatible with aromatic solvents. Suitable oxygenated solvents include propylene glycol monomethyl ether acetate, propylene glycol probyl ether acetate, ethyl ethquin propionate, dipropylene glycol monomethyl ether acetate, ethyl ethoxyprobionate, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , diethylene glycol mononityl ether acetate, dibasic acid ester (DuPon
Mixtures of esters of dibasic acids sold by T.
, ethyl acetate, n-7'-pyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate,
mixtures of hexyl acetates, such as Exxon Ch
e+r+1cal Company KaroExxate@
600 trade names, mixtures of heptyl acetates, such as Exxon Chemical C
Commercially available products under the trade name 700, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl hebutyl ketone, isophorone, impropatol, n-butanol, sec-butanol. Nonoveisobutanonobeamyl alconobeisoamyl alcohol, hexanol, and heptatool. The above list should not be construed as limiting the invention, but as examples of solvents useful in the invention.

The type and concentration of solvent is selected to provide a formulation viscosity and evaporation rate suitable for application and baking as a coating. Typical solvent concentrations are 0 to about 75% by weight;
Preferably it is about 5-50% by weight, and most preferably about 10-40% by weight. For the production of high solids coatings, the amount of solvent used in the coating formulation is preferably less than 40% of the weight of the formulation.

Preferences for the formulations of the present invention 5) Baking methods vary widely and are not limited to low temperature baking for about 20 to 30 minutes at a temperature of 200 to 220°F for large equipment applications; 600~ for coil coating application
A high temperature bake is performed at 700°F air for about 5-10 seconds. Generally, the substrate and coating should be performed at a temperature high enough for a long enough time to allow substantially all of the solvent to evaporate from the film and for the reaction between the polymer and crosslinker to proceed to the desired degree of completion. . The desired degree of completion varies over a wide range and depends on the combination of specific cured film properties required for a given application; the required baking conditions; and the type and concentration of catalyst added to the formulation. It also depends on the thickness of the applied coating film. In general, the higher the catalyst concentration, the easier it is to produce thinner films and coatings.
That is, lower temperatures and/or shorter bake times can be cured.

Acid catalysts can be used to cure systems containing hexamethoxymethylmelamine and other amino crosslinkers, and a variety of suitable acid catalysts are known to those skilled in the art. These include, for example, p-toluenesulfonic acid, methanesulfonic acid, nonylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid,
Included are phosphoric acid, phenyl phosphate, butyl phosphate, butyl maleate, and the like, as well as compatible mixtures thereof. These acid catalysts can be used in their pure unblocked form or in conjunction with suitable blocking agents such as aminos. Examples of typical non-blocking catalysts include the trade name Kani-Cure®
The K+ng Industries,
Inc.

The products include: Examples of blocked catalysts include:
The King whose trade name is NACLIRE(R)
Industries, Inc.

Catalyst usage typically varies inversely with the severity of seizure conditions. In particular, lower concentrations of catalyst are usually required if the bake-out is at a higher temperature or the bake-out is longer. Moderate burn-in condition (275
Typical catalyst concentrations for 15-30 minutes at °F are:
The catalyst solids may be about 0.3-0.5% by weight of the polymer and crosslinker solids. For lower temperature or shorter time cures, higher concentrations of catalyst, up to about 2% by weight, can be used; for higher temperature or longer time cures, an acid catalyst is required. Not considered.

For formulations of the present invention containing hexamethoxymethylmelamine as the crosslinking agent and p-)luenesulfonic acid as the catalyst, the preferred curing conditions to obtain a dry film thickness of about 1 ml are about 0. Catalyst concentration of ~0.6% by weight (solids per layer of polymer and crosslinker solids), 25
A bake temperature of 0 to 400 degrees Fahrenheit and a bake time of about 5 to about 60 minutes. Most preferable curing conditions: Well, 0
A catalyst concentration of ~0.3% by weight, a bake temperature of about 300-350°F, and a bake time of about 20-40 minutes.

As mentioned above, the liquid polymer vehicle of the present invention is characterized by improved weatherability. However, further improvements in this and other properties can be achieved by formulation with stabilizers and stabilizer systems. Compounds that improve weather resistance include) IALS (steric amino light stabilizer), UV screeners, antioxidants, etc. The liquid polymer vehicle can also be loaded with various pigments to obtain the desired color. When pigments are added to the coating formulation, the ratio of pigment to ester phenol capped polymer or polyol and amino crosslinker is desirably about 0.5:1.0-2.
0:L, 0, preferably about 0.8:1.0-L, 1L,
It is O. Another compounding means to improve weatherability is silicone resins, which are used to replace a portion of the basic polymeric material as well as to impart better weatherability to the overall system.

All of these formulation approaches can be used in the liquid polymer vehicle of the present invention.

The following examples are intended to illustrate the invention:
It is not intended to limit the invention.

Example 1 The following example illustrates the production of polyester diols by a typical method.

Mechanical stirrer, heating mantelpiece nitrogen sparger, Dean Stark trap
222 g of phthalic anhydride (PA), 219 g of Adipic acid (A,
U, 468 g of neopentyl glycol (NPC), and 200 g of Aromatic 150 solvent (a narrow-cut solvent for aromatic liquids having 9 to 12 carbon atoms, commercially available from Exxon Company, USA). Heat the contents until melted, stir, and heat to about 16°C, the temperature at which solvent/water azeotropic evaporation begins.
Continue until 0℃. fi'7) remove the solvent from the Dean-Stark trap and return it to the flask. Water removal is used to monitor the reaction. Heating continues and the temperature increases as water is removed to a final temperature of 207°C. Once the theoretical amount of water has been removed (requires 8 hours), the reaction is stopped. Cool the product and pressurize it from the container. The product is N
The VM (non-volatile content) was 84.1%, the acid number was 5.8, the hydroxylation was 168, and the reduced viscosity was 0.058 in a 10% solution in glacial acetic acid. This polyester diol can be abbreviated as: N
PG/AA/PA=3/1/1° Other similar polyester diols are prepared by simply substituting monomers, monomer ratios, and solvents.

Example 2 The following example describes the preparation of an ester phenol-capped polyester (PHBA/NPG/
The production of AA/PA) gives a highly colored product, indicating the formation of large amounts of phthalic anhydride in the second step due to decomposition of the polyester diol backbone.

Phthalic anhydride (740 g, 5.0 mol), adipic acid (730 g, 5.0 mol), neopentyl glycol (
1560g, 15.0mol), and xylene (130g
) is placed in a 51-40 flask equipped with a thermometer, heating mantle, and a Starcy and Dean-Stark trap driven by an air motor. Place a reflux condenser on top of the Dean-Stark trap and bring to reflux. A weak stream of nitrogen (40 cc/min) is passed through the reactor system. Heat the solid and begin stirring once the solid begins to melt. When the anti-core temperature reaches 150°C, water begins to be produced. The temperature slowly rises to 230°C over 7 hours.

Gas chromatographic analysis of the aqueous overhead confirmed neopentyl glycol to be azeotropic with water under these conditions. The reaction mixture was refluxed at 230° C. for a further 6 hours, after which the solvent was distilled off. The nonvolatile content (NVM) of the product is less than 97% (1 hour at 150 °C
). Oxidation is 1.4 ■KOR/g. Aqueous O/N7
- Analysis of the head revealed that neopentyl glycol 168
It was shown that g was lost by evaporation. The final NPG/AA/PA total composition ratio of oligoester diols is 2.68/1/l. Total yield: 41 g of H. The IR and low acid number show that only a small amount of PA remains.

A portion of the above oligoester diol (2293 g) was added to the same apparatus, and PHBA (1537 g>, p-TSA
(7,6g), and Aromatic 150 (
364g). The effluent gas is passed through a small column containing a DOrienete (water trap) followed by an Ascarite.
Pass it through the (mouth 02 trap). Heat the slurry while stirring.

Water production occurs below about 190°C. Is the temperature 9 hours?
The temperature slowly rises to 230℃. The reaction mixture is maintained at 230°C for an additional 9 hours to complete the esterification.

Yield is 3979g. The non-volatile content (1 hour at 150°C) is 82%. The Gardner color of the product is 14. The infrared spectrum shows that 14% (by weight) of phthalic anhydride is present dissolved in the product.

13ONMR confirmed the amount of phthalic anhydride in the product. Approximately 0.2% of the added PHBA (based on captured CO2) is decarboxylated during the reaction.

Example 3 The following example shows an improved lower temperature and lower amount of P.
A one-step method for producing an ester phenol-capped polyester is shown that yields a low-color product containing only A.

In an apparatus similar to that used in Example 1, 312 g of NPs were added.
C, 290 g p-hydroxybenzoic acid (PHBA)
, namely 148g of PA, 148g of FA, '146g of A, A (PHB A / N P G / A
A/PA: 2/3/1/l), and Aror
natic 100 solvent 200g (Mixxon Co
mpany [a narrow-cut C8-C10 aromatic solvent marketed by JSA].

The flask and its contents are heated to melt and stir, and then heated to a temperature at which solvent water azeotropy begins and distillation occurs.
Continue until 0℃. The solvent is then returned to the reaction flask,
Water production was used to monitor the reaction. Heating continued and the temperature increased as water was removed. After 2 hours, the conversion is 58% and the temperature is 175° C., with a significant decrease in water removal rate and temperature rise. Removing 60 g of solvent from the system to accelerate the reaction significantly increased the rate of temperature rise and water removal. After another 4 hours, the temperature is 1
94°C and the conversion based on water removal is 8 of the theoretical amount.
It became 7%. Then, during a further 8 hours, the temperature rose to 19
The temperature rose to 8℃. Conversion is essentially quantitative. The product in the flask is cooled to about 180°C and 60g of Arom
Atic 100 is added to reduce viscosity.

NVM is 76.4%, phenolic hydroxyl value is 1
29, the acid number is 28.3, and the reduced viscosity is 0.055 for a 10% solution of (7) in glacial acetic acid.

The Gardner color is 1 or more. The IR and NMR spectra contain the desired structure and show only a small amount (approximately 0.4% by weight) of phthalic anhydride in the product.

Other polymers can be made by similar methods by varying the amount and/or type of monomers. Other solvents may also be used. Depending on the change, the temperature/time relationship may differ somewhat.

Example 4 The following example demonstrates the production of an improved, low temperature, two-step ester phenol capped polyester.

The same apparatus as used in Example 1 was used except that the flask was changed to 51. 1092g NPC, 1050
g of PHBA, and 400 g of Aromatic 10
0 solvent (an aromatic narrow-cut solvent having 7 to 9 carbon atoms, commercially available from Exxon Company [1,S,8). 17, which is the temperature at which the flask and its contents begin to undergo solvent/water azeotrope and evaporation.
Continue heating to 0°C. 1 at a temperature of 170℃ to 180℃
It is held for 1 hour, during which time 137 g of the aqueous layer evaporates. Cool the flask and its contents to room temperature and charge 511 g of AA and 518 g of PA to the reaction vessel. Thereafter, the flask and its contents are heated to 170-198° C. for 13 hours, and 203 g of the aqueous layer is removed. Cool the system to about 160't:
544 g of Aromatic 100 solvent are added and the resulting mixture is cooled to room temperature. NVM is 73.6
%, the acid value is 42.3%, and the phenolic hydroxyl value is 101. The IR and NMR spectra contain the proposed ester phenol keyed polyester structure. Coloration is very low and there is very little PA in the product.

Example 5 The following example shows the production of an ester phenolic key polyester by a one-step process with the modification of increasing the reaction temperature during the final step of the reaction to increase the reaction rate.

The same equipment used in Example 3 was equipped with a 1050H
of PHBA, 511 g of AA, 518 g of PA, 109
Add 2g of NPC and 150g of xylene. Heat the flask and its contents until melted and begin stirring;
Heating is then continued to 154° C., the temperature at which the solvent/water azeotrope begins to distill. The temperature is gradually increased to 200° C. over 5 hours and 267 g (82% of theory) of water are removed. Continue heating to 230°C over 6 hours, then 5 more hours.
Remove 9g of water. Water removal is essentially quantitative. The product is cooled to 150° C. and 675 g of xylene are added. Cool the contents to room temperature and remove from the container. NVM is 7
The pH value is 5.9%, the acid value is 23, the phenolic hydroxyl value is 105, and the amount of CD2 generated is 2.7%.
Compatible with decarboxylation of BA.

Example 6 Example 6 below illustrates the use of different catalysts in the synthesis of ester phenol key polyesters.

The synthesis method is the same as described in Example 2, using several different catalysts at different concentrations as shown below. The reaction temperature, reaction time and conversion amount are also shown below.

Example 7 The examples below demonstrate the preparation of clear coating formulations.

A typical clear formulation is made by adding the following ingredients to a clean glass bottle (or metal can).

Esthetics similar to those described in Example 2 20.6 g lephenol-capped polyester resin (non-volatile content 76.6 g)
5%) Hexamethoxime such as Cyo+el-303 5
, 2g methylmelamine (HMMM) Methyl amyl ketone 1.8g Methyl ethyl ketone 1.8gn-Bu
3yk-o diluted to 25% in OH, 6gChe
mie Product VP-451 (Aminoplotter catalyst, 4.45% active p-TSA after dilution with n-BuOH) Total 30.0 g Then close or seal the bottle or can and place on roller. mix until a homogeneous solution is obtained (approximately 30
minutes). After mixing, the bottle or can can be left for about an additional 30 minutes to remove any air bubbles. The solution is then prepared for application onto a metal test panel via a drawdown rod or loading dock device. This particular solution exhibits the properties calculated below.

Non-volatile content 70% by weight Cymel
~” 3Q3 (HMMM) Binder solid content (25% by weight of polyester + f (M-ding) Catalyst 0.13 of binder solid content
Weight % p-TSA Similar formulations are made using many different polyester resins or ester phenol capped polyesters. Another variant is the use of binder solids at a concentration of 18-40 wt.
catalytic amounts of amino-blocked p-TSA, potassium neodecanoate, phosphoric acid or phosphorous acid catalyst, various solvents such as xylene, EXXATE 8600 (εxxon Ch
(mixture of hexyl acetate commercially available from Cornpany), n-butanobe Aro
matic 100, Aromatic 150, methyl amyl ketone and methyl ethyl ketone, and 0-0.1% by weight of now Corni based on the total formulation
Contains a stock solution of ng 57 flow control agent.

For more viscous resins, the method changes slightly to bottle the polyester resin and solvent first.

The diluted resin solution is warmed in a steam bath and mixed on rollers until a homogeneous solution is obtained.

After the solution has cooled to room temperature, the remaining ingredients are added and the complete formulation is mixed again on the roller until a homogeneous solution is obtained.

Example 8 The examples below describe the production of colored paints.

Colored paints are generally Byk-Chemie DISP
It is produced by milling titanium dioxide (T10□) in a clear solution using a high speed disk disperser such as the ERMAT @Model CV. first T
The mill base containing ie2, polyester resin or ester phenol capped polyester resin and solvent is milled and then the mill base is left with the remaining ingredients of the formulation. Specific weights for an example paint are shown below.

Mill Base: Ester Phenol Capped Poly 300g Ester Resin (Same resin as described in Example 2, but with N VM of 85°5%) Tie, (DuPont Tl-PURE@R-96
0) 300 g xylene
20g complete formulation: Mill base 220g ester phenolic resin 9.6g ester resin (85.5% non-volatile content) Cymel-” 303 (HMMM)
3 L 1 gByk-Chemie Product
VP-451 (Ami 2.Ogn block p-
TSA) EXXATE @ 700 Solvent (Exxon Chem
ica 2 L, 7 g A mixture of heptyl acetate marketed by Company) Xylene 29.7 g This particular pigment has a non-volatile content of 75.5% by weight and contains pigment/
The binder weight ratio is 0.8 and HM? vl M 1
11 degrees is 24% by weight of the binder, p-TSA
is 0.27% by weight of the catalyst amount based on the binder.

20-35% by weight of different resins, binders HMM
degree of MI, catalytic amount of aminoblock p from 0 to 0.6% by weight
- TSA, potassium neodecanoate or phosphoric acid catalyst,
A pigment with a pigment/binder ratio of 0, 8 to L 1, and Ar
omatic 100, Aromatic150, xylene, n-butanol, EXXATE@600 solvent,
Other coatings can also be made using a variety of solvents, including EXXATE 700 solvent, mixtures of methyl amyl ketone and methyl ethyl ketone.

It is shown that several commercially available pigment wetting agents/dispersants have shown significant improvements in coating properties. Improvement in hardness is approximately 7~
9 Knoop hardness units, and retention of the overall impact test value was observed. Furthermore, the weatherability of the ester phenol capped polymer was surprisingly improved. After 306 hours in the QUV tester, the initial gloss of the ester phenol-capped polymer was retained about 60-80%, whereas
Only 11-15% of the gloss of the uncapped polymer was retained.

Example 12 The following example demonstrates the effect of curing conditions on the hardness and impact strength of transparent films.

The ester phenol-capped polyester was prepared by a method similar to that used in Example 2.
Produced with a monomer ratio of A/P HB A of 3/1/1/2. A clear formulation of this resin contains 0.25% catalyst (
blocked p-TSA) and various amounts of crosslinker (H
Produced by the method of Example 7 using MM-1).

Transparent panels were manufactured by the method of Example 9, and then the different formulations were cured under various conditions of firing time and temperature. The hardness and back impact values of various panels are shown in Table 2. As the firing time or firing temperature increases,
Typically, this results in increased hardness and decreased backside impact strength.

Table ■0.33 300 10 14.8
1600.33 40
18.5 1600.33 350
10 19.4 1400.33
40 25.6 1100.5
325 10 18.4
1600.5 40 21
．． 3 600.25 325 10
12.4 00, 25
40 12.4 2*Bond
rite 01000 Panel Example 13 The following example shows the effect of catalyst amount on transparent film properties.

A resin similar to that described in Example 12 was prepared using Cymel-
”/polymer ratio of 0.35/1 and catalyzed with three different amounts of p-TSA.
It was baked at 0'F for 30 minutes and its mechanical properties were measured. 1st
As shown in the table, reducing the amount of catalyst does not affect hardness relatively, but increases backside impact strength.

Table 1 0.8 19.4 45 0.4 20.1 80 0.2 18.1 160 Example 14 The following example shows the effect of amounts of Cymel''~303 on the properties of transparent films.

The same resin as in Example 13 is formulated with a constant amount of p-TSA catalyst (0.8%) and varying amounts of Cymel'-303 crosslinker. 1 clear panel at 350°F
Bake for 5 minutes and measure mechanical properties.

As shown in Table 1, the backside impact strength decreased, but the hardness was not affected.

Table ■0, 35 20.5 3200, 50
19.7 160 Example 15 The following example lists several other ester phenol capped polyester resins that have been synthesized.

Several other ester phenol capped polyester resins were synthesized by the methods of Examples 2 and 3 and are listed in Table 1.

Table 1 2 2 0.5 0.5 0 568
1982 2.51.5 0 0
665 1692 2.5 1. L2 0.38
0 673 1672.13 1
0 1 792 1422.15 2
0 2 1240 91 (1)
IPA = Isophthalic Acid Example 16 The following example shows that different curing catalyst systems can result in very different transparent film properties, and that changes in these film properties can vary depending on the resin system used. shows.

An ester phenol-capped KH polyester similar to Example 12 and a blend of 60% of the same material and 40% of the corresponding uncapped polyester diol are prepared. Each material was mixed with 33% Cymel “ゝ～303,
Formulated with an aromatic/alcoholic solvent mixture and applied to a cooled rolled steel panel using a drawdown rod at a thickness sufficient to give a 1 mil fired clear film, the coating was then applied to a cooled rolled steel panel at 350°F for 30 minutes. Fire. Three formulations were prepared for each accessory system, with different catalyst systems, namely (1) p-
) Luenesulfonic acid (p-TSA) (0.0% of binder)
(14%), (2) none, and (3) 0.5% by weight of potassium neodecanoate were used. As shown in Table 1, the base catalyst system is superior in terms of hardness and impact strength for pure ester phenol capped polyester. However, when blending ester phenol-capped polyesters with non-chip polyester diols, the base-catalyzed system gave the poorest results;
The best results are achieved with non-catalytic systems. The optimal choice of catalyst system depends on the resin system, which will vary from system to system.

Example 17 The following example describes a method for making isophthalic acid containing an ester phenol capped polyester by a stepwise addition technique.

NPG (3,Q monope 312g), isophthalic acid (IP
A > (1,0 mol, 166 g) and 130 g of Arom
The atic 150 is placed in a 2β 40 flask equipped with a stirrer driven by an air motor, a heating mantle, a temperature system and a 10 inch column packed with 20 g of 60 diameter glass beads with a Dean-Stark trap on top. Dean 5tark reflux condenser
Place on top of plastic wrap and reflux. Flow a weak stream of nitrogen (40 cc/min) through the reactor system. Distillate gas is D
Pass through a small column containing rierite (water trap) followed by a column packed with Ascarite (CO□ trap). When the slurry is heated, water, Aroma
An azeotrope involving tic 150 and neopentyl glycol begins at 195°. Add the mixture until all the IPA is in solution (
Heating for about 3 hours until a clear yellow solution), the temperature rises to about 200°C. Approximately 70 g of aqueous layer is collected in the reaction stage.

Cool the solution and add AA (10 mol, 146 g) to the reactor.
and PHBA (2.0 mol, 276). The aqueous evaporate obtained in the first stage and containing some azeotropic NPG is placed in a 125-drop addition funnel attached to the reactor. The reaction mixture is then heated to about 165° C., during which time the aqueous evaporates return to the reactor and return to the NPC, and water is separated from the evaporates. When all the aqueous evaporates are recycled, the temperature is gradually increased to 250° C. The loss of neopentyl glycol during the reaction due to evaporation is monitored by the evaporation and residual amount of a small sample of the aqueous evaporates. Neopentyl glycol lost during synthesis is replaced on new material to maintain the desired stoichiometry. When more than 95% of the theoretical amount of water has been removed, the product is cooled and the total addition rate of introduced acid is determined by potentiometric titration using methanol as solvent. PHB
The amount of decarboxylation in A is the CD collected during the reaction.

Calculated based on the weight of and shown in Table 2 of Example 18.

Example 18 The following example demonstrates the production of several IPAs containing ester phenolic key polyesters.

IPAs coated with several different ester phenols, including polyesters, are prepared by the method of Example 17. The backbone of the polyester diol contains three monomers in varying proportions: IPA, AA and NPC. Increasing the ratio of NPG to the total amount of diacids
Decreasing the molecular weight of the ester phenol-capped polyester diol and changing the AA and IPAO ratios changes the flexibility of the system. Some syntheses are carried out using phosphoric acid catalysts, while others are carried out without any catalyst at all. The results, including the acid value of the product, the amount of PHBA decarboxylated during the synthesis, the non-volatile content of the final product, and the Gardner color are shown in Table 2.

Example 19 The following example shows that a blend of an ester phenol capped polyester and a corresponding polyester diol backbone that can be derived therefrom has better transparent film properties than the pure ester phenol cap polyester.

A polyester diol is prepared as shown in Example 1 using a monomer composition of NPG/AA/PA: 3/1/l. Furthermore, the corresponding ester phenol-capped polymers were added to PHBA/NPG/AA/PA:
Produced in the same manner as in Example 3 using 2/3/1/1.

The formulation then consists of 80% ester phenol capped polyester diol and 20% polyester diol. This formulation was mixed with 25% Cymel ”3
0.03 and 0.6% potassium neodecanoate to produce clear panels and bake at 350°F for 30 minutes.

A pure ester phenol-capped polyester diol was blended with 25% Cymel" 303 and 0.15% p-TSA to produce a transparent panel and 350°
Bake for 15 minutes at F. The formulation and firing method will be different as they will be adjusted to suit each system. Several tests were conducted on the panel, and the results are shown in Table 2. The results show that the formulation system is superior.

Table ■ Knoop hardness 23 21 Pencil hardness
4H5H Direct impact value 26 >160 Back impact value 3 >160 Flexibility - 1/8 1/8 Adhesion
58 5B Chemical resistance 10% HCβ Very good Very good 10%
NaOH Poor Very good Distilled water Very good Very good Methyl ethyl chloride
Excellent Very good xylene
Excellent Very good 5alt Spra
y(Fog) 8 10 Humidity
109 Weather resistance 27 11 Permeability
14.8 15.6MEK Rubs
> 250 78* Bonder i
te■1000 Panel Example 20 The following example shows the formulation of an ester phenol capped polyester with several commercially available resins.

The polymer blend of Example 19, consisting of a polyester and a polyester diol, is compounded with several commercially available coating resins to determine whether satisfactory films can be obtained. Commercially available resins are, for example, acrylic resins, short or long oil alkyd resins, epoxy/phenolic resins, epoxy/acrylic resins, aromatic and aliphatic urethane resins, nitrocellulose resins, chlorinated rubbers and other polyester resins.

In each case, the blend of ester phenol capped polyester system and commercially available resin was 1:10 to 1 by weight solids.
0:1 and commercially available resins are made by suitably combining them with clear formulations. The formulation obtained from Example 19 was formulated as shown in Example 19,
Clear formulations of commercially available resins are prepared without any pigments and are recommended by those skilled in the art.

All solutions are first checked for incompatibility (turbidity or separation). Draw off what is compatible, dry at room temperature, and check compatibility again. To restore the compatible system, the film is then pulled down and baked using the method of the main resin component. Formulations that produce a clear, non-tacky cured film after this baking/drying are considered to be compatible. Table 1 shows specific commercially available resins and their compatibility.

Manufacturer (1) NL Chemicals (2J Rohm & Haas (3) C1ba Geigy (4) Borden Chemical (5) Re
1chhold Chemical (6) Mobay
Che+n1cal(7) Hercules, I
nc.

Example 21 The following example shows that blending a small amount of ester phenol capped polymer with a commercially available alkyd resin improves the chemical resistance of the alkyd.

A non-liquid crystal ester phenol-capped polyester was prepared according to the manufacturing method of Example 2 to prepare PHB A/NPG/AA.
/PA: Produced using 2/3/1/1. This material (80 parts) was then mixed with the corresponding uncapped polyester diol (NPC/AA/PA: 3/
1/1) and 20 parts.

This modified ester phenol cap mixture was then mixed with a commercially available alkyd resin (NL Chemical
^roplaz■6235) which is marketed and sold by s.
and 89% by weight of alkyd resin and 11% by weight of modified ester phenol. The formulation was mixed with 26% Cymel"303.0.4
Blend with 7% p-TSA, aromatic/alcohol solvent mixture and prepare panels as described in Example 9. The resulting panels are compared to panels made from alkyd resin without the use of ester phenol resin.

Table X shows the results of the chemical resistance tests and shows the significant improvement of the formulated panels.

Example 22 The following example shows that in order to obtain good mechanical properties, Tg
Shows the importance of including <40 ester phenol capped polyesters.

Three different ester phenol-capped polyester diols, shown in Table XI as EPCPl, EPCP2 and EPCP3, were synthesized by the method of Example 3 and
PEDIOLL (NPG/AA/PA:
3/1/1: Tg=-11℃) and PEDIOL2
(NPG/PA: 4/3: Tg=33℃)
Two polyester diols designated as are prepared by the method of Example 1. The Tg of the resin is Torsiona
l Braid analysis. Some of the resins are
Compounded with each other to produce separate resins. resin/
The formulation is 33% Cymel TX3 without curing catalyst.
03, applied to the panel and baked at 350°F for 30 minutes. The results are as shown in Table XI, Tg<
The resin or resin blend at 40°C forms a transparent film with a good combination of hardness and impact resistance, but
Resins or resin blends with Tg>40°C have high hardness, but
Indicates the formation of a film with substantially no backside impact strength.

Example 23 The following example illustrates a method for making an ester phenol block acrylic resin.

Into 11 flasks equipped with a stirrer, a heated clover, a Dean 5tark trap, and a nitrogen purge system, the monomer composition was hydroxyethyl methacrylate (2).
400 g of acrylic resin (NVM 66.7%) is 8.4 mol%, 23.6 mol% styrene, and 48.6 mol% butyl acrylate. Then add 0.3 g p-TSA and 86.2 H PHBA in 100 g xylene and disperse nitrogen into the system (approximately 40 c
c/min) 0 When the mixture is heated with stirring, water evolution begins at about 166°C. After a further 5 hours of heating time, the theoretical amount of 8
1% water is produced. Cool the product to room temperature and transfer. The phenolic hydroxyl value is 102 ■KOH/g polymer, and the aliphatic hydroxyl value is 19.3 gKOH/g polymer.

Example 24 The following example demonstrates the preparation of the color formulation and the properties of the panels produced thereby.

An ester phenol capped polyester/polyester diol formulation similar to that described in Example 18 was prepared with titanium dioxide pigment, LCI dispersant 5OLSPERSε
24 (100) and Dow Corning 57 flow control agent. The formulation is prepared by the method described in Example 7 according to the following formulation.

MILL BASε (weight basis) Polyester diol (solid content 71.4%) 7.5SO
LSPER3ε24000 solution (solid content 24%) 2.5
Ti02 (DuPont Tl-PIIRE' R-
960> 3 1.7L
ET-DOWN (by weight) Ester phenol cap polyes 27.5 tildiol (solid content 73.6%) Polyester diol (solid content 71.4%) 5,7H!
J? , (M(American Cyanamid C
ymel~303) 14.8Dow Corni
ng 57 (diluted to 25 0.3% by weight in n-butanol) n-butanol 7.8A
romatic 100
7.2 Total amount (weight basis)
A 100.0 panel is drawn down as described in Example 8 and baked at 350'F for 30 minutes. The film is then evaluated using a method similar to that described in Example 9. The following combinations of properties are obtained:

Knoop hardness number 13 Direct impact test >160 (lb) Back impact test 93 (lb) 20 degree gloss initial * 72 After 250 hours Quv 36 Example 25 The following example shows that an alkali metal salt of a weak base undergoes an esterification reaction. PHBA catalyzes the decarboxylation of PHBA.

A polyester diol is prepared as in Example 2. The BA samples are then reacted with diols containing various amounts of potassium salts of PHB A, which are prepared by neutralizing PHBA with KOH and evaporating the water contained. The reaction with the sample is carried out as follows: 1138 g of polyester diolbe 92H PHBA, an appropriate amount of potassium salt of PHBA,
and 50 g of Aromatic 150 into eleven 40 flasks equipped with a thermometer, mechanical stirrer, heating mantle, Dean-Stark trap, and nitrogen inlet tube. Attach a reflux condenser to the top of the Dean-Stark trap. A slight nitrogen flow (40 cc/
minutes). The effluent gas is passed through a Drierite (water trap) followed by an Acarete packed column (CO2 wrap). The slurry is heated with stirring and the progress of the reaction is monitored by plotting the amount (%) of water produced versus the reaction time.

The degree of decarboxylation is determined at the end of the reaction time from the weight of the collected CD. The results are shown in Table X■. The amount of esterified PHBAO (%) is expressed as “%PHBAester/k”, and the amount of decarboxylated (%) is expressed as “P
HB A Decarb”.

The results clearly show that the higher the amount of potassium, the greater the amount of PHBA decarboxylation (destruction), accompanied by a decrease in PHBA esterification and incorporation into the ester phenol-capped oligomer.

137.8. 91.9 6 65.1 1
2.313g, 6 92.5 81 55.3
15.6142.0 94.2 1781 23
．． 6 74.6136.6 91.1 6356
10 85.7 Example 26 The following example demonstrates the preparation of an ester phenol capped simple diol.

In a device similar to that used in Example 1 but with a capacity of 11, 200 g of 1,12-dodecanediol SPHBA29
0 g, 5 g of phosphoric acid, and 100 g of xylene. The flask and its contents are heated until melted and stirred, and heating is continued to 170° C. when the solvent water azeotrope begins to flow out. The solvent is continuously returned to the reaction flask and water production is used to monitor the reaction. Continue heating and increase the temperature to remove water. After 6 hours, the conversion is 56% and the temperature is 199°C. Increase the temperature to 200-210°C.
Hold at °C for a further 21 hours. The conversion is essentially quantitative. Cool the contents and transfer. The diester, a white solid, is dissolved in acetone and precipitated by adding distilled water.

The solid material obtained is filtered and dried. The solid has a molecular weight of 440 and a phenolic hydroxyl value of 255.

Example 27 The following example demonstrates the production of an ester phenol capped polyester having a number average molecular weight of about 4000.

In a 5F 40 flask equipped with a mechanical stirrer, heating mantle, nitrogen sparger, 110 inch column with a Dean stack trap and reflux condenser on top, and a thermometer with temperature regulator, 3
94g phthalic anhydride (PA), 742g isophthalic acid (IPA), 1042g neopentyl glycol (NPC), and 150g Aromatic 100
A solvent (a narrow-cut C9 to C12 aromatic solvent commercially available from Exxon Company, USA) is introduced. Heat the contents until melted, stir and heat until the solvent/water azeotrope begins to distill out, about 1
Continue up to a temperature of 70°C. Water removal is used to maintain the reaction. Continue heating and increase the temperature further to 220°C until water is removed! - Raise to temperature. The total distillate collected is essentially a mixture of neopentyl glycol and water and is 243 g. The reaction mixture is cooled and 347 g of adipic acid (AA) and 138 g of p-hydroxybenzoic acid (PHBA) are added. The contents of the reactor are stirred and heating is continued until the temperature reaches about 140°C. The distillate collected in the first phase of the reaction is then added dropwise to the NPC to remove the water present in the distillate. Heating is continued and the temperature is slowly raised to 250° C. so that the water produced by the reaction distillate distills out. The reaction is stopped after about 19 hours, after the theoretical amount of water has been removed. The reaction product was cooled and its acid value was checked (7.0 ROM/g). after that,
The product was combined with 633 g of dithyl 3-ethoxypropionate (EEP) and Aromatic 100 solvent 510
Dilute by adding 2 g. Non-volatile content (NVM)
When measured, it was 65.5% (150℃
time). 5 of glacial acetic acid and methyl amyl ketone (MAK)
The reduced viscosity of the 10% (w/v) (7) resin in the 0150 mixture is 0.182 and the number average weight is approximately 4,000. The polyester can be abbreviated as follows.

NPG/AA/IPA/PHBA: 20/4.751
5,32/8.93/2 The coating was made as described in Example 8 and the panel was made as described in Example 9. Excellent mechanical properties, e.g. T-bend of 0, backside impact resistance greater than 200,
It exhibited a hardness of 16 Knoob, a pencil hardness of 2H, a M E K rub greater than 250, and a crosshatch adhesion of 5B.

Claims (1)

[Scope of Claims] (1) (a) A non-liquid crystal ester phenol-capped polymer represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein R is about 20
represents a polyvalent group having a number average molecular weight of 0 to about 10,000, R^1 represents a direct bond, a hydrocarbylene group having 1 to 20 carbon atoms, or an oxy group having 1 to 20 carbon atoms; Represents a hydrocarbylene group, and R^2 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms. and n represents an integer from 2 to 10), and (b) an amino crosslinker in an amount effective to cure an ester phenol capped polymer. (2) The glass transition temperature of the ester phenol-capped polymer is from about -40°C to about 40°C.
1) The liquid polymer composition described above. (3) The liquid polymer composition according to claim 2, wherein R has a number average molecular weight of about 200 to 6,000. (4) The liquid polymer composition according to claim 2, wherein R^1 represents a direct bond and R^2 represents a hydrogen atom. 5. The liquid polymer composition of claim 2, wherein the aliphatic hydroxy- or epoxy-functional polymer is a polyester, alkyd resin, acrylic copolymer, or epoxy resin. (6) the ratio of active crosslinking groups of the amino crosslinker to phenolic groups of the ester phenol cap polymer is about 1;
．． Claims in the range of 0:1.0-15.0:1.0 (
5) Liquid polymer composition as described. (7) The liquid polymer composition of claim (6), wherein the aliphatic hydroxy-functional polymer is a polyester. (8) The liquid polymer composition according to claim (7), wherein R has a number average molecular weight of about 200 to 3,000. (9) The liquid polymer composition according to claim (5), wherein the ester phenol-capped polymer, which is not a liquid crystal, is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 is a hydroxy-terminated polyester produced from a condensation reaction product of at least one type of polyhydric alcohol and at least one type of polybasic acid or acid derivative. 2 whose derived number average molecular weight is about 200-1500
Represents a valence group. ) (10) At least one polyhydric alcohol is neopentyl glycol, ethylene glycol, propylene glycol, butanediol, hexamethylene diol,
Cyclohexaline methanol, trimethylolpropane, or pentaerythritol, and at least one polybasic acid or acid derivative is isophthalic acid, phthalic anhydride, terephthalic acid, adipic acid, succinic acid, glutaric acid, fumaric acid, azelaic acid. , sebacic acid, dimer acid, maleic acid, cyclohexanedicarboxylic acid, trimellitic anhydride, pyromellitic dianhydride, or hexahydrophthalic anhydride. 11. Claim 1 further comprising an amount of solvent effective to bring the viscosity of the coating to about 10 centipoise to 100 poise, the amount of solvent being less than 40% by weight of the liquid polymer composition. The liquid polymer composition described. (12) The liquid polymer composition according to claim (1), further comprising an alkali metal salt or alkaline earth metal salt of a weak acid in an amount effective to catalyze the crosslinking reaction. (13) The liquid polymer composition of claim (1) further comprising a catalytically effective amount of an acid catalyst selected from alkyl or aromatic sulfonic acids or blocked alkyl or aromatic sulfonic acids. 14. The liquid polymer composition of claim 1, further comprising at least one pigment in an amount effective to provide a desired coloration to a film or surface coating made from the liquid polymer composition. (15) A solid crosslinked polymer composition produced by curing the liquid polymer composition of claim (1). (16) The liquid polymer composition according to claim (1), further comprising at least one of the following polymer compounds. (a) Polymers having at least two aliphatic hydroxy or epoxy functional groups. (b) A non-liquid crystal, ester-phenol functionalized polymer represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, each R^1 independently represents a direct bond, or a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms. represents a carbylene group, and R^2 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom,
C1 -C4 alkyl, C1 -C4 alkoxy or C1 -C4 alkoxycarbonyl, and R^3 is at least two aliphatic hydroxy or epoxy functional groups; Represents a monovalent group having a number average molecular weight of about 200 to 10,000 derived from a polymer having the group. (c) a second polymer having a number average molecular weight of about 200 to 10,000 having at least two aliphatic hydroxy or epoxy functional groups. (d) A second non-liquid crystalline ester phenol functionalized polymer having the formula of claim (1). (17) The glass transition temperature of the polymer component mixture is about -3
17. The liquid polymer composition of claim 16, wherein the temperature is from 0<0>C to about 35<0>C. (18) The liquid polymer composition according to claim 16, wherein R has a number average molecular weight of about 200 to about 3,000. (19) The liquid polymer composition according to claim 16, wherein R^1 represents a direct bond and R^2 represents a hydrogen atom. (20) The liquid polymer composition according to claim (16), wherein the polymer compound (a) is represented by the following formula: HO-R^3-OH, and the polymer compound (b) is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 is a hydroxy-terminated polyester produced from a condensation reaction product of at least one type of polyhydric alcohol and at least one type of polybasic acid or acid derivative. 2 whose derived number average molecular weight is about 200-1500
Represents a valence group. ) (21)(a) A non-liquid crystal, ester phenol-capped polymer represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a polyvalent group derived from a polyhydric alcohol having 12 to 40 carbon atoms, and R^1 represents a direct bond or the number of carbon atoms. represents a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms, and R^2 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom number (1 to 4 alkoxy groups, or C1 to C4 alkoxycarbonyl groups, and n is an integer from 2 to 10), and (b) an amount of amino crosslinking effective to cure the ester phenol-capped polymer. A liquid polyol composition comprising a homogeneous mixture of agents. (22) The liquid polyol composition according to claim (21), further comprising at least one type of polyol compound below. (a) Polyhydric alcohol having 12 to 40 carbon atoms. (b) An ester phenol functionalized polyol represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1 represents a direct bond, a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms, R^2 represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms, and R^7 is Represents a monovalent group derived from a polyhydric alcohol having 12 to 40 carbon atoms.) (c) A second polyhydric alcohol having 12 to 40 carbon atoms. (23) An effective amount of an aliphatic hydroxy- or epoxy-functional polymer can be expressed using the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R represents a polyvalent group derived from an aliphatic hydroxy- or epoxy-functional polymer) , R^1 represents a direct bond, a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms, and R^2 is a hydrogen atom, a hydroxyl group, a halogen atom, or a carbon atom. represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 10. (a) having at least two aliphatic hydroxy or epoxy functional groups and having a number average molecular weight between 200 and 10,00;
1. A method of improving the surface properties of a film, or a film or surface coating, produced by curing a liquid film-forming or coating formulation comprising a polymer that is 0.0 or less, and (b) an amino crosslinker. (24) The glass transition temperature of the mixture of polymer components is about 4
The method according to claim 23, wherein the temperature is below 0°C. 25. The method of claim 23, wherein the amount of ester phenol-capped polymer replacing the polymer is about 5% or more by weight of the polymer in the original liquid film-forming or coating formulation. (26) The method according to claim (23), wherein R has a number average molecular weight of about 200 to about 6,000. (27) The method according to claim (23), wherein R^1 represents a direct bond and R^2 represents a hydrogen atom. (28) The method of claim 23, wherein the aliphatic hydroxy or epoxy functional polymer is a polyester, alkyd resin, acrylic copolymer or epoxy resin. (29) The ratio of active crosslinking groups of the amino crosslinker to the phenolic groups of the ester phenol cap polymer is approximately 1.
The method according to claim (23), wherein the ratio is 0:1.0 to 15.0:1.0. (30) The method of claim (23), wherein the aliphatic hydroxy-functional polymer is a polyester. (31) The method of claim 30, wherein the number average molecular weight of R is between about 200 and 3000. (32) The method according to claim (23), wherein the non-liquid crystal, ester phenol-capped polymer is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 is a hydroxy-terminated polyester produced from a condensation reaction product of at least one type of polyhydric alcohol and at least one type of polybasic acid or acid derivative. 2 whose derived number average molecular weight is about 200-1500
Represents a valence group. ) (33) At least one type of polyhydric alcohol is neopentyl glycol, ethylene glycol, propylene glycol, butanediol, hexamethylene diol, cyclohexalinemethanol, trimethylolpropane,
or pentaerythritol, and at least one polybasic acid or acid derivative is isophthalic acid, phthalic anhydride, terephthalic acid, adipic acid, succinic acid, glutaric acid,
33. The method according to claim 32, wherein the acid is fumaric acid, azelaic acid, dibasic acid, dimer acid, maleic acid, cyclohexanedicarboxylic acid, trimellitic anhydride or pyrometic anhydride. (34) The method of claim (23), wherein the polymer is further replaced with an ester phenol functionalized polymer represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, each R^1 independently represents a direct bond, or a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms. represents a carbylene group, and R^2 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom,
C1 -C4 alkyl, C1 -C4 alkoxy or C1 -C4 alkoxycarbonyl, and R^5 is at least two aliphatic hydroxy- or epoxy functions. Represents a monovalent group having a number average molecular weight of about 200 to 10,000 derived from a polymer having the group. (35) The method according to claim (34), wherein R has a number average molecular weight of about 200 to about 3,000. (36) The method according to claim (34), wherein R^1 represents a direct bond and R^2 represents a hydrogen atom. (37) The aliphatic hydroxy- or epoxy-functional polymer is a polyester,
35. The method according to claim 34, wherein the resin is an alkyd resin, an acrylic copolymer, or an epoxy resin. (38) The method according to claim (34), wherein the ester phenol functionalized polymer is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 is a hydroxy-terminated polyester produced from a condensation reaction product of at least one type of polyhydric alcohol and at least one type of polybasic acid or acid derivative. 2 whose derived number average molecular weight is about 200 to 1500
Represents a valence group. ) (39) Polyhydric alcohol having 12 to 40 carbon atoms and amino crosslinking, comprising replacing the polyhydric alcohol having 12 to 40 carbon atoms with an effective amount of a non-liquid crystal ester phenol-capped polyhydric alcohol represented by the following formula: A method of improving the surface properties of a film or a film or surface coating by curing a liquid film-forming or coating formulation containing an agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a polyvalent group derived from a polyhydric alcohol having 12 to 40 carbon atoms, and R^1 represents a direct bond or a number of carbon atoms. Represents a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms, and R^2 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom number. (40) The glass transition temperature of the mixture of polymer components is about 4.
The method according to claim 39, wherein the temperature is lower than 0°C. (41) The method according to claim (39), wherein R^1 represents a direct bond and R^2 represents a hydrogen atom. (42) The method according to claim (39), wherein the non-liquid crystal, ester phenol capped polyhydric alcohol is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^4 represents a divalent group derived from a diol having 12 to 40 carbon atoms) (43) A polyhydric alcohol having 12 to 40 carbon atoms further 43. The method of claim 42, wherein the ester phenol is substituted with a phenol-functionalized polyhydric alcohol of the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a direct bond, a hydrocarbylene group having 1 to 20 carbon atoms, or an oxyhydrocarbylene group having 1 to 20 carbon atoms, and R ^2 represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms, and R^7 is (44) The method of claim 43, wherein the mixture of polyol components has a glass transition temperature of less than about 40°C. (45) The method according to claim (43), wherein R^1 represents a direct bond and R^2 represents a hydrogen atom. (46) for producing a hydroxybenzoic acid-capped polymer having the formula Method. ▲Mathematical formulas, chemical formulas, tables, etc.▼ (wherein R is about 20
Represents a polyvalent group having a number average molecular weight of 0 to about 10,000, R^2 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. , or an alkoxycarbonyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 10. (47) The method according to claim 46, wherein the hydroxybenzoic acid is p-hydroxybenzoic acid. 48. The method of claim 46, wherein the esterification reaction mixture contains up to about 0.2% by weight of an alkali metal or alkaline earth metal salt of a weak acid. 49. The method of claim 46, wherein the esterification reaction mixture comprises a catalytically effective amount of a strong acid catalyst selected from alkyl or aromatic sulfonic acids or blocked alkyl or aromatic sulfonic acids. (50) Claim (46) wherein the aliphatic hydroxy-functional polymer is synthesized in situ by reacting a C2-C8 polyhydric alcohol with a polybasic acid or acid derivative in the presence of hydroxybenzoic acid. ) method described. 51. The method of claim 50, further comprising the step of esterifying the remaining aliphatic hydroxy functional polymer by increasing the final reaction temperature to 200° C. or higher. (52) reacting a 1 molar excess of a C2-C8 polyhydric alcohol with hydroxybenzoic acid at a reaction temperature below about 200°C, thereby partially esterifying the polyhydric alcohol; a reaction mixture of a partially esterified polyhydric alcohol and a C 2 -C 8 polyhydric alcohol, maintained at a temperature of 20
A method for producing a hydroxybenzoic acid capped polymer represented by the following formula, comprising reacting with an effective amount of at least one polybasic acid or acid derivative to achieve a number average molecular weight of 0 to 10,000. ▲Mathematical formulas, chemical formulas, tables, etc.▼ (wherein R is about 20
represents a polyvalent group having a number average molecular weight of 0 to about 10,000, R^1 represents a direct bond or has 1 to 2 carbon atoms;
0 hydrocarbylene groups, or 1 to 2 carbon atoms
0 represents an oxyhydrocarpylene group, and R^2 is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. represents a carbonyl group, and n represents an integer of 2 to 10. 53. The method of claim 52, wherein the molar ratio of C2-C8 polyhydric alcohol to hydroxybenzoic acid is within the range of about 1:1 to 10:1. (54) The method according to claim (52), wherein the hydroxybenzoic acid is p-hydroxybenzoic acid. 55. The method of claim 52, wherein the esterification reaction mixture contains about 0.2% by weight or less of an alkali metal or alkaline earth metal salt of a weak acid. (56) The method of claim (52), wherein the esterification reaction mixture comprises a catalytically effective amount of a strong acid catalyst. (57) Hydroxybenzoic acid-capped polyhydric alcohol represented by the following formula, which includes a step of directly esterifying a large amount of polyhydric alcohol having 12 to 40 carbon atoms with an effective amount of hydroxybenzoic acid at a reaction temperature of about 200°C or less. A method for producing alcohol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R represents a polyvalent group derived from a polyhydric alcohol having 12 to 40 carbon atoms, and R^2 represents a hydrogen atom, hydroxyl group, halogen atom, or 1 carbon atom. represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 10.)