JP2005290214A - Polyhemiacetal ester resin, manufacturing method, resin composition, and hardened resin article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition providing a hardened article excellent in chemical and physical properties and having an excellent storage stability, and to provide a rosin derivative suitable for preparing the thermosetting composition. <P>SOLUTION: Hydroxy groups and cyclic anhydride groups are converted into a half ester in a reaction of a rosin alcohol with a chemical compound having in each molecule one cyclic anhydride group and one carboxyl group or with a chemical compound having in its molecule two cyclic anhydride groups. Further, to the carboxyl groups generated in this way, a divinyl (thio)ether compound is added for the generation of the polyhemiacetal ester resin in an addition reaction. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyhemiacetal ester resin derived from rosin alcohol, that is, a hydroxy compound derived from rosin, a production method thereof, a resin composition, and a cured product obtained by curing the resin composition.

Rosin is a natural resin obtained by processing rosin and containing abietic acid, neoabietic acid, parastrinic acid, levopimaric acid and the like as active ingredients. For this reason, the burden on the environment is small compared to petrochemical products and the like, and it is widely used for ink resins, tackifiers, paint binders, soldering fluxes, and the like. Although rosin is crystalline and has low melt viscosity and exhibits very excellent properties as a thermoplastic resin, it has not been used as a curing agent for thermosetting resins.
There are also known rosin derivatives such as maleopimaric acid and acrylopimaric acid obtained by addition reaction (Diels Alder reaction) of conjugated diene resin acid component of rosin with maleic acid or acrylic acid (Patent Document 1). Since the carboxyl group is directly bonded to the tertiary carbon of the bulky hydrophenanthrene skeleton, it is difficult to react with a reactive resin such as an epoxy resin due to its steric hindrance. Use as is difficult.

  On the other hand, Patent Documents 2 and 3 disclose a polyhemiacetal ester resin obtained by reacting a carboxyl group of a dicarboxylic acid compound with divinyl ether and a thermosetting composition containing the same. The polyhemiacetal ester resin regenerates free carboxyl groups at a relatively low temperature to give a cured product excellent in chemical performance, physical performance, weather resistance, etc., but there is a limit to improving the physical properties of the cured product. That is, the glass transition temperature of the exemplified polyhemiacetal ester resin is about 30 to 40 ° C. at the maximum, and it is difficult to use it as a powder type thermosetting composition. In fact, when applied to powder coatings, there is a problem that blocking occurs under storage conditions of 30 ° C.

JP-A-5-86334 European Patent Application No. 643,112 JP-A-7-82351

A first object of the present invention is to provide a novel polyhemiacetal ester resin that can be used for ink resins, powder coatings, soldering fluxes, and the like.
The second object of the present invention is to provide a method for producing the polyhemiacetal ester resin.
Furthermore, the third object of the present invention is to provide a thermosetting composition using the polyhemiacetal ester resin.
Moreover, the 4th objective of this invention is to provide the hardened | cured material formed by hardening | curing the said thermosetting composition, and an application.

  As a result of intensive studies to develop the polyhemiacetal ester resin, the present inventors have obtained a compound having one cyclic acid anhydride group and one carboxyl group in one molecule in the hydroxyl group of rosin alcohol. Alternatively, a polyhemiacetal ester resin obtained by subjecting a compound having two cyclic acid anhydride groups in one molecule to a ring-opening half-esterification reaction, and further reacting a divinyl (thio) ether compound with the generated carboxyl group However, the inventors have obtained knowledge that the object can be achieved, and have completed the present invention.

That is, the present invention includes the following [1] to [8].
[1] For ring-opening half esterified products of rosin alcohols and compounds having one cyclic acid anhydride group and one carboxyl group in one molecule, or compounds having two cyclic acid anhydride groups in one molecule And a polyhemiacetal ester resin having a weight average molecular weight of 1,000 to 1,000,000 obtained by addition reaction of a divinyl (thio) ether compound.
[2] The polyhemiacetal ester resin according to claim 1, which has a group represented by the following formula (1) or (2) as a repeating unit, and the number of the repeating unit is 2 to 500.

[Wherein R ¹ is a trivalent organic group having 1 to 50 carbon atoms, R ² is a divalent organic group having 1 to 50 carbon atoms, Y ¹ is an oxygen atom or a sulfur atom, ¹ represents a residue of rosin alcohol. ]

[Wherein R ³ is a tetravalent organic group having 1 to 80 carbon atoms, R ⁴ is a divalent organic group having 1 to 50 carbon atoms, Y ² is an oxygen atom or a sulfur atom, and ² represents a residue of rosin alcohol. ]

[3] The process for producing a polyhemiacetal ester resin according to [1] or [2], wherein the following step I and step II are performed.
Step I: Half-esterification of a compound having one cyclic acid anhydride group and one carboxyl group in one molecule or a compound having two acid anhydride groups in one molecule on the alcoholic hydroxyl group of rosin alcohol Process.
Step II: Further, a step of adding a divinyl (thio) ether compound to the generated carboxyl group.
[4] The method for producing a polyhemiacetal ester resin according to [3], wherein a base catalyst is used as a catalyst in the reaction of the step I.
[5] A component; the polyhemiacetal ester resin according to [1] or [2];
B component; The thermosetting composition characterized by containing the compound which has 2 or more of the reactive functional groups which can form a chemical bond with a carboxyl group in 1 molecule.
[6] The thermosetting composition according to the above [5], further comprising a component C; an acid catalyst.
[7] The thermosetting composition according to [5] or [6], wherein the acid catalyst of component C is a heat latent acid catalyst that exhibits activity during heat curing.
[8] A cured resin product obtained by curing the thermosetting composition according to any one of [5] to [8].

  According to the present invention, there is provided a polyhemiacetal ester resin that has a rosin skeleton and is excellent in solubility in various organic solvents and resins. Moreover, the thermosetting resin composition which is excellent also in storage stability is provided by mix | blending the polyhemiacetal ester resin of this invention. Furthermore, by curing the thermosetting resin composition of the present invention, a cured resin product excellent in chemical performance and physical performance is provided.

Hereinafter, the present invention will be described in detail.
The polyhemiacetal ester resin of the present invention uses rosin alcohol and a compound having one cyclic acid anhydride group and one carboxyl group in one molecule, or a compound having two cyclic acid anhydride groups in one molecule. Then, the hydroxyl group of rosin alcohol and the cyclic acid anhydride group are subjected to a half esterification reaction, and the resulting carboxyl group is further subjected to an addition reaction with a divinyl (thio) ether compound.
The polyhemiacetal ester resin of the present invention is more preferably a resin having a group represented by the following formula (1) or (2) as a repeating unit, and the number of the repeating unit is 2 to 500. .

Here, R ¹ is a trivalent organic group having 1 to 50 carbon atoms, R ² is a divalent organic group having 1 to 50 carbon atoms, Y ¹ is an oxygen atom or a sulfur atom, and A ¹ Represents a residue of rosin alcohol.

Here, R ³ is a tetravalent organic group having 1 to 80 carbon atoms, R ⁴ is a divalent organic group having 1 to 50 carbon atoms, Y ² is an oxygen atom or a sulfur atom, and A ² Represents a residue of rosin alcohol.

The polyhemiacetal ester resin of the present invention can be produced by the following method.
That is, as the reaction of Step I, a compound having one cyclic acid anhydride group and one carboxyl group in one molecule on the hydroxyl group of rosin alcohol, or a compound having two cyclic acid anhydride groups in one molecule Then, as a reaction of Step II, a compound obtained by the reaction of Step I is used as a starting material, and a divinyl (thio) ether compound is added to a newly generated carboxyl group of this compound. Is added to obtain the polyhemiacetal ester resin in which the carboxyl group is blocked.
The series of two-stage reactions may be performed sequentially, or may be continuously performed in the same reaction vessel without once recovering the intermediate reactant.

Next, the raw material used for manufacture of the polyhemiacetal ester resin of this invention is demonstrated.
The rosin alcohol used in the present invention is obtained by hydrogenating the carboxyl group of various rosins into a hydroxymethyl group. As the rosin alcohol, for example, hydroabietyl alcohol, abiethyl alcohol, dehydroabietyl alcohol, dihydroabietyl alcohol, tetrahydroabietyl alcohol, neoabietyl alcohol, pimalyl alcohol, isopimaryl alcohol, levopimaryl alcohol, Sandaracopimalyl alcohol, parastryl alcohol and the like can be mentioned. These rosin alcohols can be used alone or as a mixture of two or more.

Compounds having one cyclic carboxylic anhydride group and one carboxyl group in one molecule include trimellitic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (hydrogenated anhydride). Compounds such as trimellitic acid).
Examples of the compound having two or more cyclic carboxylic anhydride groups in one molecule include pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic acid Aromatic carboxylic acid anhydrides such as anhydrides, ethylene glycol bis (anhydro trimellitate), glycerol bis anhydro trimellitate monoacetate, diphenylsulfone tetracarboxylic dianhydride; butane tetracarboxylic dianhydride Aliphatic carboxylic anhydrides; 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy- And alicyclic carboxylic acid anhydrides such as 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.
Among these cyclic acid anhydrides, butanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5 -(2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4 -Anhydride (hydrogenated trimellitic anhydride) is preferably mentioned from the point of availability and the solubility of the resulting thermosetting rosin derivative in solvents and resins.
These raw materials can be used alone or in combination of two or more.

  Examples of the divinyl (thio) ether compound include compounds represented by the following formula (3).

_{^{H 2 C = CH-Y 3}} -R 5 -Y 3 -CH = CH 2 ··· (3)
[Wherein R ⁵ is a divalent organic group having 1 to 50 carbon atoms, and Y ³ is an oxygen atom or a sulfur atom. ]

  Examples of the divinyl (thio) ether compound represented by the formula (3) include aliphatic divinyl ether, aliphatic divinyl thioether, aromatic divinyl ether, and aromatic divinyl thioether. Specifically, for example, trimethylene glycol Divinyl ether, 1,4-bisvinyloxymethylcyclohexene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,5-pentanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,4-cyclohexane dimeta Aliphatic divinyl ethers such as divinyl ether; aromatic divinyl ethers such as 1,4-benzene divinyl ether, bisphenol A divinyl ether and bisphenol F divinyl ether; and corresponding aliphatic divinyl thioether compounds and aromatic divinyl thioethers Compounds.

Among the divinyl (thio) ether compounds described above, 1,4-butanediol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether, which are aliphatic divinyl ethers, are available and the carboxyl group produced in Step I Preferred from the viewpoint of reactivity with.
These raw materials can be used alone or in combination of two or more.

Next, the steps I and II will be described.
First, in the ring opening half-esterification reaction between the hydroxyl group of rosin alcohol and cyclic acid anhydride in Step I, 1 mol of cyclic acid anhydride group reacts with 1 mol of hydroxyl group, and the cyclic acid anhydride group Is a reaction in which 1 mol of a free carboxyl group is formed. This ring-opening half-esterification reaction can be performed by a method known per se, for example, in an organic solvent at a temperature range of room temperature to 200 ° C.

The use ratio of rosin alcohol and cyclic acid anhydride in the ring-opening half esterification reaction in Step I can be arbitrarily selected according to the purpose, but usually, cyclic acid anhydride per mole of hydroxyl group of rosin alcohol. It is suitable to use a cyclic acid anhydride so that the physical group is usually 0.2 to 2 mol, preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol.
In the ring-opening half esterification reaction in Step I, a catalyst such as an organic amine compound can be used to accelerate the reaction. Specifically, examples of such a catalyst include methylamine, ethylamine, butylamine, s-butylamine, t-butylamine, amylamine, octylamine, cyclohexylamine, vinylmethylamine, allylamine, ethoxymethylamine and the like. Primary amines; secondary amines such as dimethylamine, diethylamine, dipropylamine, diallylamine, dihexylamine, didodecylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine; ethanolamine, diethanolamine, triamine Alkanolamines such as ethanolamine; benzines such as phenylpropylamine, phenylethylamine, methoxybenzylamine, diethylbenzylamine, benzylamine, dimethylbenzylamine Aliphatic amines having a ring; morpholine derivatives such as morpholine and methylmorpholine; aniline derivatives such as t-butylaniline; aromatic amines such as dimethyltoluidine; 2-hydroxypyrimidine, 2-hydroxypyridine, 3-hydroxypyridine, Pyridine derivatives such as 4-hydroxypyridine; piperidine derivatives such as piperidine, methylpiperidine, benzylpiperidine; pyrrolidine derivatives such as methylpyrrolidine; pyrrole derivatives such as pyrrole; 2-hydroquinoline, 3-hydroquinoline, 4-hydroquinoline, 2 -Quinoline derivatives such as methylquinoline and 4-methyl-8-hydroquinoline; imidazole derivatives such as benzimidazole, methylimidazole and imidazole; tetramethylammonium hydroxide, tetraethylan Quaternary ammonium salts such as triphenylsulfonium hydroxide, and the like.
Further, organotin compounds such as dibutyltin laurate and butyltin oxyacetate can also be used as a catalyst for promoting the reaction.
The said catalyst can be used individually by 1 type or in mixture of 2 or more types.
The amount of the catalyst used is preferably 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of rosin alcohol and cyclic acid anhydride as raw materials. Part.

Next, the reaction in Step II will be described.
In this reaction, a polyhemiacetal ester resin containing a rosin skeleton of the present invention is obtained by adding a divinyl (thio) ether compound to the ring-opened half esterified product obtained in the above step I.
This addition reaction can be performed by a method known per se, for example, at a temperature of room temperature to 200 ° C.

  The ratio of the ring-opening half-esterified product and the divinyl (thio) ether compound used in the addition reaction in Step II can be arbitrarily selected according to the purpose, but usually the carboxyl group 1 produced by the ring-opening half-esterified product. It is suitable to use the divinyl (thio) ether compound so that the vinyl (thio) ether group is 0.2 to 2 mol, particularly 0.5 to 1.5 mol, per mol.

  In the blocking reaction in Step II, an acid catalyst can be used for the purpose of promoting the reaction. Examples of such an acid catalyst include acidic phosphoric acid esters represented by the following formula (4).

[Wherein R ⁶ is an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, and h is 1 or 2. ]
More specifically, primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol, and isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclo Examples thereof include phosphoric acid monoesters or phosphoric acid diesters of secondary alcohols such as hexanol.
The said catalyst can be used individually by 1 type or in mixture of 2 or more types.

The amount of the acid catalyst to be used is not particularly limited, but it is usually based on 100 parts by weight of the total amount of the compound obtained by subjecting the hydroxyl group of rosin alcohol to a ring-opening half esterification reaction with a cyclic acid anhydride and a divinyl (thio) ether compound. 0.0005 to 5 parts by weight is preferable, and 0.001 to 1 part by weight is particularly preferable.
Although depending on the use of the polyhemiacetal ester resin to be synthesized and the blending system selected, the acid value is usually 30 mgKOH / g or less. More preferably, it is 10 mgKOH / g or less, More preferably, it is 3 mgKOH / g or less.
In particular, when the polyhemiacetal ester resin of the present invention is used for a flux or a solder paste, a lower acid value of the resin is more preferable in storage or the like because it is more stable.

Furthermore, for the purpose of lowering the acid value of the polyhemiacetal ester resin of the present invention, a monovinyl (thio) ether compound can be further reacted with the carboxyl group at the end of the resin. In addition, monovinyl (thio) ether means monovinyl ether or monovinyl thioether.
Specific examples of the monovinyl (thio) ether compound include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, t-amyl vinyl ether, 2- Alkyl vinyl ethers such as ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether; hydroxyethyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, hydroxybutyl vinyl ether, ethylene Glycol monovinyl ether, hexanediol monovinyl ether And vinyl ethers containing hydroxyl groups such as diethylene glycol monovinyl ether; alkylene glycol alkyl vinyl ethers such as ethylene glycol butyl vinyl ether and triethylene glycol methyl vinyl ether; other vinyl ethers such as aminopropyl vinyl ether, diethylaminoethyl vinyl ether and propenyl ether propylene carbonate And the corresponding vinyl thioethers.

Among the monovinyl (thio) ether compounds, n-propyl vinyl ether and n-butyl vinyl ether are preferable from the viewpoint of availability and reactivity. These monovinyl (thio) ether compounds can be used alone or in combination of two or more.
The monovinyl (thio) ether compound is usually used in an amount of 0.05 to 0.5 mol with respect to 1 mol of the divinyl (thio) ether compound which is an essential component of the present invention.

The reaction ratio at the time of reacting the terminal carboxyl group of the polyhemiacetal ester resin with the alkyl vinyl ether or alkyl vinyl thioether compound is an equivalent ratio {(carboxyl group) from the remaining amount of unreacted substances and physical properties with respect to the resin. / Vinyl ether) equivalent ratio} is usually 1.0: 1.0 to 1.0: 5.0, preferably 1.0: 2.0 to 1.0: 5.0.
When the equivalent ratio is less than 1.0: 1.0, the alkyl vinyl ether or the alkyl vinyl thioether is less preferable because the acid value of the polyhemiacetal ester resin does not decrease, and the equivalent ratio is 1.0: 5.0. A larger amount is not preferable because a large amount remains as an unreacted substance.
Moreover, reaction temperature should just be the temperature of the range of normal room temperature-200 degreeC normally, Preferably, it is room temperature-150 degreeC. The reaction time for this reaction may be appropriately selected according to the progress of the reaction, but it is usually 1 to 100 hours.

In each of the reactions of the two steps, an organic solvent can be used for the purpose of making the reaction system uniform and facilitating the reaction. Examples of such organic solvents include benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.), Solvesso # 150 (Exxon Chemical Co., Ltd.) Aromatic hydrocarbons such as (registered trademark); ethers such as dioxane and tetrahydrofuran; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, propylene glycol Esters and ether esters such as monomethyl ether and methoxybutyl acetate; acetone, methyl ethyl ketone, diisobutyl ketone, diethyl ketone, methyl propyl ketone, diisopropyl ketone, methylamylohexanone, isophorone, mesityl oxide , Ketones such as methyl isoamyl ketone, ethyl n-butyl ketone and ethyl amyl ketone; phosphate esters such as trimethyl phosphate, triethyl phosphate and tributyl phosphate; and aprotic polarities such as dimethyl sulfoxide and N, N-dimethylformamide Solvent: Triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, dipropylene glycol, diethylene glycol-2-ethylhexyl Ether, tetraethylene glycol dimethyl ether Glycol derivatives such as Le like.
More preferably, propylene glycol monomethyl ether acetate is used.
The said organic solvent can be used individually by 1 type or in combination of 2 or more types. Although the usage-amount of the said organic solvent is not specifically limited, It is 5-95 weight part normally with respect to 100 weight part of reaction raw materials in each reaction step, Preferably, it is 20-80 weight part.
In all the two-stage reactions, the same or different organic solvents can be used, and in the reaction in the subsequent step II, a method such as distilling off part or all of the solvent used in the previous stage. Or may be used as it is without being removed, or by further adding a solvent.

Further, the thermosetting resin composition of the present invention contains the polyhemiacetal ester resin of the present invention as the A component and a compound having two or more groups that react with a carboxyl group as the B component in one molecule. Regarding the mixing ratio of the A component and the B component, the equivalent ratio of the free carboxyl group generated when the A component is heated and cured and the functional group of the B component chemically bonded to these functional groups by heating is 0.1: 0. It is preferable to contain each component so that it may become the ratio of equivalence ratio 0.2: 0.8-0.8-0.2. Furthermore, it is preferable to contain each component so that it may become a ratio of equivalent ratio 0.3: 0.7-0.7-0.3 as a powder coating application. When the equivalent ratio of the A component and the B component is out of the range, the heat curing becomes insufficient, and the mechanical properties of the obtained cured product and molded product may be lowered, which is not preferable.
The polyhemiacetal ester resin of the present invention can be used as it is or by mixing a general-purpose thermoplastic resin such as a polyester resin, an acrylic resin, a vinyl chloride resin, or a polyvinyl ether resin.
Moreover, as B component, the compound which has 2 or more groups which react with a carboxyl group in 1 molecule may be used individually by 1 type, and 2 or more types may be combined.

As the compound of component B used in the present invention, when the polyhemiacetal ester resin regenerates a free carboxyl group by heating, two or more reactive functional groups that can react with this to form a chemical bond, preferably Can be blended with 2 to 50 compounds in one molecule.
The reactive functional group is not particularly limited as long as it has a property of reacting with a carboxyl group, and examples thereof include an epoxy group, an oxetane group, an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, and an amino group. Preferred examples include groups, imino groups, isocyanate groups, blocked isocyanate groups, cyclocarbonate groups, vinyl ether groups, vinyl thioether groups, aminomethylol groups, alkylated aminomethylol groups, acetal groups, and ketal groups. One type of these reactive functional groups may be contained in B component, and 2 or more types may be contained. More preferably, an epoxy group, an oxetane group, an oxazoline group, etc. are mentioned.

Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl Examples include epoxy group-containing compounds such as homopolymers or copolymers such as methyl (meth) acrylate, and further include epoxy group-containing compounds such as polyglycidyl compounds obtained by reaction of polycarboxylic acids or polyols with epichlorohydrin. It is done. More preferably, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are mentioned.
Furthermore, the condensate of the compound represented by Formula (5) is mentioned.

_{^{(R 7) k -Si- (OR}} 8) 4-k ··· (5)
(In the formula, R ⁷ and R ⁸ are each an alkyl group or aryl group having 1 to 18 carbon atoms, and k is 0, 1 or 2.)
Furthermore, homopolymers or copolymers of α, β-unsaturated silane compounds such as acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-butoxysilane, and compounds of these compounds Silanol group and alkoxysilane group-containing compounds such as hydrolysis products; α, such as aliphatic polyols, phenols, polyalkyleneoxy glycols, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Hydroxyl group-containing compounds such as homopolymers or copolymers of β-unsaturated compounds, and ε-caprolactone adducts of these polyols; aliphatic and aromatic diamino compounds and polyamino compounds, and cyanos of the polyols An amino group-containing compound such as a polyamino compound obtained by reducing an ethylation reaction product; an imino group-containing compound such as an aliphatic or aromatic polyimino compound; p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3 ′ -Dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, methylene bis (phenyl isocyanate), lysine methyl ester diisocyanate, bis (Isocyanate ethyl) fumarate, isophorone diisocyanate, methyl cyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and the same An isocyanate group-containing compound such as an adduct compound of these isocyanates and the polyol; phenols, lactams, active methylenes, alcohols, acid amides of the isocyanate group-containing compounds; Blocked isocyanate group-containing compounds such as imides, amines, imidazoles, ureas, imines, and oximes; homopolymers or copolymers of 3- (meth) acryloyloxypropylene carbonate, the epoxy A cyclocarbonate group-containing compound such as a polyvalent cyclocarbonate group-containing compound obtained by reacting a group-containing compound with carbon dioxide; a polyvalent compound obtained by reacting the polyvalent hydroxyl group-containing compound with a halogenated alkyl vinyl ether. Vinyl ether compounds, polyvinyl ether compounds obtained by reaction of hydroxyalkyl vinyl ethers with polyvalent carboxyl group-containing compounds and the above polyisocyanate compounds, copolymers of vinyloxyalkyl (meth) acrylates with α, β-unsaturated compounds Vinyl ether compounds such as vinyl thioether compounds and vinyl thioether compound-containing compounds such as melamine formaldehyde resin, glycolyl formaldehyde resin, urea formaldehyde resin, aminomethylol group and alkylated aminomethylol group-containing α, β -An aminomethylol group or alkylated aminomethylol group-containing compound such as a homopolymer or copolymer of an unsaturated compound; a polyvalent ketone, a polyvalent aldehyde compound, the polyvalent vinyl Polyacetal compounds obtained by reaction of ether compounds and the like with alcohols and orthoacid esters, condensates of these with polyol compounds, and further vinyloxyalkyl (meth) acrylates with alcohols and orthoacid esters Examples include acetal group and ketal group-containing compounds such as homopolymers or copolymers of adducts.

Examples of the compound containing an oxazoline group include 1,2-bis (2-oxazolin-2-yl) ethane, 1,4-bis (2-oxazolin-2-yl) butane, and 1,6-bis (2 -Oxazolin-2-yl) hexane, 1,8-bis (2-oxazolin-2-yl) octane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazoline) -2-yl) benzene, 1,3-bis (2-oxazolin-2-yl) benzene, 1,4-bis (2-oxazolin-2-yl) benzene, 1,2-bis (5-methyl-2) -Oxazolin-2-yl) benzene, 1,3-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,4-bis (4,4-dimethyl-2-oxazolin-2-yl) benzene Etc. It is below.
As a commercial item of the compound containing the above oxazoline group, for example, Nippon Shoku Kagaku Co., Ltd., a product name “1-5 mol% of 2-ethyl-2-oxazoline copolymerized with an acrylic monomer” There are "Epocross K-1000" and "Epocross K-2000" series (number average molecular weight 70,000 to 80,000) and the like, which can be preferably used.

Examples of the compound containing an oxetane group include 3-alkyl-3-hydroxymethyloxetanes having an alkyl group having 1 to 8 carbon atoms such as 3-methyl-3-methoxymethyloxetane and 3-ethyl-3-methoxymethyloxetane. The following oxetane compounds derived from (i) and (ii) can be preferably used.
(I) Etherified product of hydroxyl compound and 3-alkyl-3-hydroxymethyloxetane Specifically, for example, an aliphatic monoalcohol composed of an alkyl group having 1 to 6 carbon atoms, an alkylene group having 2 to 8 carbon atoms An aliphatic glycol comprising 2 to 18 carbon atoms, a phenol novolak resin, a hydroxyl compound such as a polysiloxane having a quaternary structure and a polymerization degree of 2 to 8, and 3-ethyl-3-methoxymethyl Examples include compounds obtained by ether condensation of oxetanes such as oxetane. More specifically, for example, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene 4,4′-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) biphenyl, 3,3 ′, 5,5′-methyl-4,4′-bis (((3-ethyl-3 -Oxetanyl) methoxy) methyl) biphenyl, 1,4-bis ((3-ethyl-3-oxetanyl) methoxy) benzene, 4,4'-bis ((3-ethyl-3-oxetanyl) methoxy) biphenyl, 3, And 3 ′, 5,5′-methyl-4,4′-bis ((3-ethyl-3-oxetanyl) methyl) biphenyl.

(Ii) Esterified product of carboxyl compound and 3-alkyl-3-hydroxymethyloxetane Specifically, for example, a carboxyl compound such as (meth) acrylic acid, carbonic acid, adipic acid, terephthalic acid, cyclohexanedicarboxylic acid, and 3 Examples include compounds obtained by esterifying oxetanes such as -ethyl-3-methoxymethyloxetane, and more specifically, for example, (3-ethyl-3-oxetanyl) methyl methacrylate, bis ((3-ethyl-3- Oxetanyl) methyl) carbonate, bis ((3-ethyl-3-oxetanyl) methyl) adipate, bis ((3-ethyl-3-oxetanyl) methyl) benzene-1,4-dicarboxylate, bis ((3-ethyl -3-oxetanyl) methyl) cyclohexane-1,4-dicarboxylate Etc. The.
Among these compounds containing an oxetane group, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] biphenyl is preferably mentioned from the viewpoint of the physical properties of the resin cured product.
The said compound containing an oxetane group can be used individually by 1 type or in mixture of 2 or more types.

The compound of B component may be mix | blended individually by 1 type, and may be mix | blended in combination of 2 or more type. However, in this case, a combination showing an active action when the respective functional groups are combined is not preferable because storage stability is impaired.
Examples of such an unfavorable combination include a combination of a functional group selected from an epoxy group, an isocyanate group, a vinyl ether group, a vinyl thioether, a cyclocarbonate group and a silanol group with an amino group or an imino group, and an isocyanate. -A combination of a thio group or a vinyl ether group and a hydroxyl group.

The thermosetting composition of the present invention can contain an acid catalyst for the purpose of promoting the curing reaction. Examples of such acid catalysts include protonic acids such as halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono and diesters, polyphosphoric acid esters, boric acid mono and diesters; BF ₃ , FeCl ₃ , Organometallic compounds such as SnCl ₄ , AlCl ₃ , ZnCl ₂ , trialkyl boron, trialkyl aluminum, dialkyl aluminum halide, monoalkyl aluminum halide, tetraalkyl tin; diisopropoxyethyl acetoacetate aluminum, tris (ethyl acetoacetate ) Aluminum, isopropoxybis (ethyl acetoacetate) aluminum, monoacetylacetonato bis (ethyl acetoacetate) aluminum, tris (n-propyl acetoacetate) al Minium, tris (n-butylacetoacetate) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, acetylacetonatobis (propionylacetonato) ) Aluminum, diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetonato) titanium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethyl acetoacetate) ) Zirconium, dichloro-bis (acetylacetonato) tin, dibutyl-bis (acetylacetonato) tin, tris (acetylacetonato) iron, Metal chelate compounds such as tris (acetylacetonato) chromium, tris (acetylacetonato) rhodium, bis (acetylacetonato) zinc, tris (acetylacetonato) cobalt; dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, Magnesium naphthenate, calcium naphthenate, manganese naphthenate, iron naphthenate, cobalt naphthenate, copper naphthenate, zinc naphthenate, zirconium naphthenate, lead naphthenate, tin naphthenate, calcium octylate, manganese octylate, octylate Iron, cobalt octylate, copper octylate, zinc octylate, zirconium octylate, lead octylate, tin octylate, lead laurate, magnesium stearate, aluminum stearate, stearyl Calcium acid, cobalt stearate, zinc stearate, and Lewis acids such as metal soaps such as lead stearate. These acid catalysts can be used alone or in combination of two or more.

Furthermore, the thermosetting composition of the present invention, in some cases, maintains good long-term storage stability and promotes the curing reaction when cured in a short time at a low temperature, resulting in good chemical performance in the cured product. In addition, for the purpose of imparting physical performance, a thermal latent catalyst exhibiting activity during heat curing can be contained.
The thermal latent acid catalyst is preferably a compound that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. When this heat-latent acid catalyst exhibits acid catalyst activity at a temperature of less than 60 ° C., the resulting composition may cause an undesirable situation such as thickening during storage or gelation. Specifically, a compound (i) obtained by neutralizing a protonic acid with a Lewis base, a compound (ii) obtained by neutralizing a Lewis acid with a Lewis base, a mixture (iii) of a Lewis acid and a trialkyl phosphate, sulfonic acid esters ( Preferable examples are iv), phosphate esters (v), onium compounds (vi), and compounds (vii) derived from aluminum complexes.

Examples of the compound (i) obtained by neutralizing the protonic acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric monoesters, phosphoric mono- and diesters, polyphosphoric esters, boric mono- and diesters, and the like. Various amines such as ammonia, monoethylamine, triethylamine, n-butylamine, cyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, piperidine, aniline, morpholine, or trialkylphosphine, triarylphosphine, trialkylphosphine. Phyto, compounds neutralized with triaryl phosphite, and Necurer 2500X, X-47-110, 3525, 5225 (trade name, King) commercially available as acid-base blocking catalysts Ndasutorizu Co., Ltd.) and the like. Examples of the compound (ii) obtained by neutralizing a Lewis acid with a Lewis base include compounds obtained by neutralizing a Lewis acid such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the above Lewis base. . Or the mixture (iii) of the said Lewis' acid and trialkyl phosphate is also mentioned. Examples of the sulfonic acid esters (iv) include those represented by the formula (6)

(In the formula, R ⁹ is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or an alkyl group, and R ¹⁰ is a carbon atom number 3 bonded to the sulfonyloxy group via a primary carbon or a secondary carbon. 18 alkyl groups, alkenyl groups, aryl groups, alkaryl groups, alkanol groups, saturated cycloalkyl groups, hydroxycycloalkyl groups, unsaturated cycloalkenyl groups, or hydroxycycloalkenyl groups. It is done.
Specific examples of the compound include sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid, and n-propanol, n-butanol, Primary alcohols such as n-hexanol and n-octanol or esterified products with secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol, and Examples include β-hydroxyalkyl sulfonic acid esters obtained by reacting sulfonic acids with oxirane group-containing compounds.
Examples of the phosphate esters (v) include the acid catalyst that can be used in Step I, that is, the compound represented by the formula (4).

Examples of the onium compound (vi) include compounds represented by formulas (9) to (12).
[(R ¹¹ ) ₃ NR ¹² ] ⁺ · X ⁻ (9)
[(R ¹³ ) ₃ PR ¹⁴ ] ⁺ · X ⁻ (10)
[(R ¹⁵ ) ₂ OR ¹⁶ ] ⁺ · X ⁻ (11)
[(R ¹⁷ ) ₂ SR ¹⁸ ] ⁺ · X ⁻ (12)
(Wherein R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁷ are each an alkyl group, alkenyl group, aryl group, alkaryl group, alkanol group or cycloalkyl group having 1 to 12 carbon atoms, and two R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁷ may be bonded to each other to form a heterocycle having N, P, O or S as a heteroatom, and R ¹² , R ¹⁴ , R ¹⁶ and R ¹⁸ are hydrogen An atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, and a compound represented by X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ^— or BF ₄ ^—. It is done.

  Further, a compound (vii) derived from an aluminum complex can be used as a catalyst. Specific examples include metal soaps such as aluminum octylate, β-diketonate aluminum complexes, β-diketoesterate aluminum complexes, and o-carbonylphenolate aluminum complexes. Examples of the β-diketone used as the ligand of the aluminum complex include 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 2,4-pentanedione, 3-phenyl- 2,4-pentanedione, 5-dimethyl-2,4-hexanedione, 5-phenyl-2,4-pentanedione, 2,6-dimethyl-3,5-heptanedione, 2,6-tetramethyl-3 , 5-pentanedione and the like.

  Examples of the β-diketoester include ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, and ethyl benzoyl acetate. Examples of o-carbonylphenol include 2-hydroxy-benzaldehyde, 2 ′ -Hydroxy-acetophenone, methyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate and the like.

Furthermore, in order to increase the activity, an aluminum complex in which a silanol compound is further mixed with the above aluminum complex may be used. Such silanol compounds include triphenylsilanol, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxy. Silane, phenyltriethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluorodecyltrimethoxysilane, triphenylmethoxysilane, And triphenylethoxysilane.
Among these catalysts, an aluminum complex mixed with a silanol compound is more preferable.

  In the thermosetting composition of the present invention, one type of catalyst may be used, or two or more types may be combined, and the blending amount thereof is 100 parts by weight of the polyhemiacetal ester resin of the present invention. On the other hand, it is usually selected in the range of 0.01 to 10 parts by weight. When the amount of the heat latent acid catalyst is less than 0.01 parts by weight, the catalytic effect is not sufficiently exhibited, and when it exceeds 10 parts by weight, the finally obtained cured product is colored or the water resistance is lowered. This is not preferable.

The thermosetting composition of the present invention is a thermoplastic resin, a solvent, a coloring pigment, a filler, an elastomer, a solvent, an ultraviolet absorber, an antioxidant, and a fluidity adjustment as necessary within the range not impairing the effects of the present invention. An agent or the like can be blended.
Specific examples of the thermoplastic resin used in the thermosetting composition of the present invention include polyester resins, acrylic resins, vinyl chloride resins, and polyvinyl ether resins.
It does not specifically limit as a solvent used for the thermosetting composition of this invention. It can be used by appropriately selecting from ordinary general-purpose solvents. Specifically, for example, the same solvent as that used for the reaction during the production of the thermosetting rosin derivative can be used. The amount added is approximately 0 to 50% by weight.

  The production of the thermosetting composition of the present invention is made by blending all components including polyhemiacetal ester resin as a main component in a lump or sequentially, a blade-type stirrer, a desolver, a kneader, a ball mill blender, What is necessary is just to mix by a normal method using a roll disperser. The mixing temperature is preferably 10 to 50 ° C. in order to avoid condensation or volatilization of the solvent, although it depends on the blending components.

The thermosetting composition of this invention can obtain a preferable resin cured material by thermosetting. There is no restriction | limiting in particular in the apparatus used for hardening, Hardening apparatuses, such as a closed-type hardening furnace and a tunnel furnace which can be continuously hardened, are employable. The heating source is not particularly limited and can be performed by a method such as hot air circulation, infrared heating, high-frequency heating or the like.
The temperature and time required for curing vary depending on the temperature at which the free carboxyl group is regenerated from the blocked carboxyl group in the polyhemiacetal ester resin, the type of catalyst, etc., but usually at a temperature in the range of 50 to 250 ° C. Curing is completed by heating for about 2 minutes to 10 hours. More preferably, the temperature is in the range of 80 to 200 ° C., and the heating is for about 10 minutes to 2 hours.

  The polyhemiacetal ester resin of the present invention regenerates a free carboxyl group under heating and forms a chemical bond with the reactive functional group of component B. In addition to this reaction, the intramolecular polarization structure As a so-called active ester, an addition reaction can be caused to the reactive functional group of the B component. In this case, since no desorption reaction is involved in the crosslinking reaction, it is possible to contribute to the reduction of emission of volatile organic substances.

  The thermosetting composition of the present invention is mounted on a color liquid crystal display device, a color video camera, etc. as a use for electronic parts in addition to general-purpose uses such as paint binders, ink resins, adhesives, tackifiers, molded products, etc. It can be used as a color filter, a photosensitive resist relating to the manufacture of IC circuits and photomasks, a soldering flux for mounting components on a mounting substrate, and a solder paste containing the flux.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these.
Next, the measurement method and evaluation method used are shown.
1. <IR measurement conditions>
Model: JASCO Corporation, FT / IR-600
Cell: Liquid membrane method using potassium bromide Decomposition; 4 cm ⁻¹
Number of integration: 16 times <Measurement of weight average molecular weight>
The weight average molecular weight (Mw) was determined in terms of polyethylene by gel permeation chromatography (GPC). The measurement conditions of gel permeation chromatography (GPC) are as follows.
Model: manufactured by Tosoh Corporation, gel permeation chromatography SC-8010
Column: SHODEX K-801 manufactured by Showa Denko K.K.
Eluent: THF solution Detection solution: RI
3. <Measurement conditions for glass transition temperature>
Model: Seiko Instruments Inc. DSC220
Temperature increase rate: 10 ° C / min
Nitrogen flow rate: 50 mL / min
4). <Measurement of acid value>
It measured according to the method of JISK0070-3 (1992).
5). <Measurement conditions for ¹³ C-NMR>
Model: Nippon Bruker Co., Ltd., 400 MHz Advance 400
Integration count: 1024 times Solvent; CDCl ₃ , TMS standard

Example 1; polyhemiacetal ester resin (R-1)
<Process I>
In a four-necked flask with a capacity of 200 mL equipped with a thermometer, reflux condenser, and stirrer, 40.7 g of rosin alcohol (Rika Hercules Co., Ltd., trade name “Abitol E”), cyclohexane-1,3, Charge 19.5 g of 4-tricarboxylic acid-3,4-anhydride (hydrogenated trimellitic anhydride) and 22.9 g of propylene glycol monomethyl ether acetate (PMA), raise the temperature to 140 ° C. and maintain the same temperature The reaction was continued for 2 hours, and the reaction was terminated when the reaction rate reached 98% by measuring the acid value of the sampled reaction solution. The rosin alcohol is composed of 14% by weight dehydroabiethyl alcohol, 36% by weight dihydroabiethyl alcohol, 33% by weight tetrahydroabiethyl alcohol, 6% by weight esters and 11% by weight hydrocarbon. is there.
<Process II>
Thereafter, the temperature in the system was lowered to 80 ° C., and 16.9 g of 1,4-butanediol divinyl ether was added dropwise at a constant rate over 30 minutes. The reaction was continued at the same temperature for 2 hours, and the reaction was terminated when the acid value of the mixture became 10 mgKOH / g or less. After cooling, reprecipitation purification of the polymer was performed with a mixed solvent of hexane / acetone = 9/1 (weight ratio). Furthermore, the rotary evaporator was used to distill off the solvent from the mixed solution, and then vacuum drying was performed with a vacuum pump to obtain 67.1 g of a light yellow transparent solid polyhemiacetal ester resin (R-1). Table 1 shows the analysis results such as the charged composition, reaction conditions, and glass transition temperature.

Examples 2, 3; Production of polyhemiacetal ester resin (R-2, R-3) React in the same manner as in Example 1 except that the charged composition and conditions were changed as shown in Table 1, Further purification yielded a light yellow transparent solid polyhemiacetal ester resin (R-2, R-3). Table 1 shows the analysis results such as the charged composition, reaction conditions, glass transition temperature, etc., as in Example 1.

The components and abbreviations in Table 1 indicate the following.
* 1) Rosin alcohol (Abitol E (trade name) manufactured by Rika Hercules Co., Ltd.)
* 2) B-4400 (5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Dainippon Ink & Chemicals, Inc. Epicron B-4400 (trade name))
* 3) PMA (propylene glycol monomethyl ether acetate)

Comparative Example 1 Production of polyhemiacetal ester resin (P-1) In a 200 mL four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 35.7 g of 1,4-cyclohexanedicarboxylic acid 1,4-cyclohexanedimethanol divinyl ether 44.3 g and propylene glycol monomethyl ether acetate 20.0 g were charged, the temperature was raised to 110 ° C., the reaction was continued for 2 hours while maintaining the same temperature, and sampled. The reaction was terminated when the acid value of the reaction solution became 10.0 mgKOH / g or less. After cooling, reprecipitation purification of the polymer was performed with a mixed solvent of hexane / acetone = 9/1. Furthermore, the rotary evaporator was used to distill off the solvent from the mixed solution, and then vacuum drying was performed with a vacuum pump to obtain 67.1 g of a light yellow transparent solid polyhemiacetal ester resin (P-1). Table 2 shows the analysis results such as the charged composition, reaction conditions, and glass transition temperature.

Comparative Example 2: Production of polyhemiacetal ester resin (P-2) In a 200 mL four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, 35.3 g of isophthalic acid and 1,4-cyclohexane Xylene dimethanol divinyl ether (43.4 g) and propylene glycol monomethyl ether acetate (21.3 g) were charged, the temperature was raised to 110 ° C., and the reaction was continued for 2 hours while maintaining the same temperature. The reaction was terminated when it reached 10.0 mgKOH / g or less. After cooling, reprecipitation purification of the polymer was performed with a mixed solvent of hexane / acetone = 9/1. Furthermore, using a rotary evaporator, the solvent was distilled off from the mixed solution, and then vacuum drying was performed with a vacuum pump to obtain 68.3 g of a light yellow transparent solid polyhemiacetal ester resin (P-2). Table 2 shows the analysis results such as the charged composition, reaction conditions, and glass transition temperature.

The structure of the polyhemiacetal ester resin containing the rosin skeleton obtained in Examples 1 to 3 was confirmed by infrared absorption spectrum measurement (IR spectrum). FIG. 1A shows an IR spectrum chart of rosin alcohol which is a raw material of the polyhemiacetal ester resin (R-1) containing a rosin skeleton of the present invention, and FIG. 1B shows an IR spectrum chart of hydrogenated trimellitic anhydride. FIG. 1C shows an IR spectrum chart of a half esterified product of rosin alcohol and hydrogenated trimellitic anhydride. Furthermore, the IR spectrum chart of the polyhemiacetal ester resin (R-1) containing the rosin skeleton obtained in Example 1 is shown in FIG. Further, figure ¹³ C-NMR chart of the rosin alcohol and water添無water 2 to ¹³ C-NMR chart of the half ester of trimellitic acid, poly hemiacetal ester resin obtained in Example 1 (R-1) 3 shows.

From FIG. 1A, rosin alcohol was confirmed to have an infrared absorption peak at 3000 to 4000 cm ⁻¹ due to the hydroxyl group. Further, from the B 1, water添無water trimellitic acid, peaks attributable to carboxyl groups, in the vicinity of 2500～3500Cm ^-1, a peak attributable to the acid anhydride structure, the 1786 cm ^-1 and 1705 cm ^-1 Each was confirmed. On the other hand, in the half esterified product of rosin alcohol and hydrogenated trimellitic anhydride, as shown in FIG. 1C, the peaks of the hydroxyl group and the acid anhydride structure derived from the above-mentioned raw materials disappear and are derived from the carboxyl group. Only the peak was confirmed. That is, through Step I, it was confirmed that the ring-opening half esterification reaction of rosin alcohol and hydrogenated trimellitic anhydride was proceeding. Furthermore, in D of FIG. 1, the peak resulting from a carboxyl group has disappeared, and the half esterified product of rosin alcohol and hydrogenated trimellitic anhydride has reacted with divinyl ether through Step II. It could be confirmed.
From the ¹³ C-NMR measurement results shown in FIG. 3, a peak due to the carbonyl carbon of the ester structure was observed at around 172 to 173 ppm, and a peak due to the hemiacetal ester structure was observed at around 95 ppm. On the other hand, in FIG. 2, since no peak due to the hemiacetal ester structure is observed, the carboxyl group of the half esterified product of rosin alcohol and hydrogenated trimellitic anhydride reacts with vinyl ether and is converted to the hemiacetal ester structure. I understand that.
From the above analysis results, it was confirmed that the polyhemiacetal ester resin (R-1) was produced after Steps I and II.

Examples 4-7
Thermosetting compositions were produced using the polyhemiacetal ester resins (R-1 to 3) obtained in Examples 1 to 3. The composition is shown in Table 2. Using the obtained thermosetting resin, a cured product was obtained by the following method.
<Method for measuring physical properties of cured film>
The test piece was prepared on a brush-polished aluminum plate that had been anodized using the resin compositions of Examples 4 to 7 described in Table 2 with a bar coater so that the dry film thickness was 50 μm. After prebaking at 80 ° C. for 30 minutes, the test piece was prepared by curing at 180 ° C. for 60 minutes.

Using the test piece of the cured film prepared by the above method, performance evaluation was performed by the following test method.
In addition, after mixing each component, the thermosetting composition obtained in Table 3 confirmed visually that there was no turbidity, generation | occurrence | production of a foreign material, and isolation | separation.
(1) Acid resistance-1
2 mL of 40 wt% sulfuric acid was placed on a spot on a test piece and allowed to stand at 20 ° C. for 48 hours, and then the abnormality of the cured film was visually determined.
(2) Acid resistance-2
2 mL of 40% by weight sulfuric acid was placed on the test piece on a spot, heated at 60 ° C. for 30 minutes, and then the abnormality of the cured film was visually determined.
(3) Acid resistance-3
The test piece was immersed in 0.1 N sulfuric acid and kept at 60 ° C. for 24 hours, and then the abnormality of the cured film was visually determined.
(4) Impact resistance Using an impact deformation tester [JIS K-5400 (1979) 613.3 B method], a test piece is placed in a shooting mold having a radius of 6.35 mm, and a 500 g weight is dropped from a height of 40 cm. The damage of the cured film at the time of making was judged visually.
(5) Tensile strength, elastic modulus Measured using an autograph AGS-H manufactured by Shimadzu Corporation.
(6) Cured film Tg (° C)
Using TMA (Seiko Instruments TMA / SS150), the temperature at which the elongation of the cured product suddenly changes when the temperature is raised at 10 ° C./min is defined as a cured film Tg (° C.).
(7) Acetone extract The remaining test piece weight (%) after extracting the test piece in acetone solvent for 3 hours was determined.
(8) Xylene wipeability The test piece was rubbed strongly with gauze moistened with mixed xylene (JIS K 2435 product), and the abnormality of the test piece surface after 10 reciprocations was visually judged.
(9) Storage stability test 10 g of the composition shown in Table 2 was hermetically stored at 50 ° C., and the state after storage for 30 days was visually observed.
These results are shown in Table 3.

The components and abbreviations in Table 3 indicate the following.
* 1) 3,4-epoxycyclohexyl-3 ′, 4′-cyclohexanecarboxylate (Delcel Chemical Industries, Ltd. Celoxide 2021P (trade name)),
* 2) Bisphenol A novolak epoxy resin (Epicoat 157S70 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.), epoxy equivalent 210 g / eq,
* 3) Biphenylbisoxetane (ETERNACOLL OXBP (trade name) manufactured by Ube Industries, Ltd.),
* 4) 80% by weight cyclohexanone solution of a zinc complex in which zinc octylate and triethanolamine are reacted in equimolar amounts,
In Examples 4 to 9, cured films having excellent transparency were obtained.

Examples 8 and 9: Application to powder coating materials The raw material components listed in Table 4 were placed in a drive render (trade name “Henschel Mixer” manufactured by Mitsui Chemicals, Inc.) and mixed uniformly for about 1 minute. Under a temperature condition of 80 to 120 ° C., melt kneading was performed using an extrusion kneader (manufactured by Buss, trade name “Busconider PR46”), and after cooling, the mixture was finely pulverized with a hammer type impact pulverizer. Next, filtration was performed using a 180-mesh wire mesh. In Example 8, a clear powder paint was obtained, and in Example 9, an enamel powder paint was obtained.
Using an electrostatic powder coating machine, the above powder coating is applied to a 0.6 mm thick molten alloyed galvanized steel sheet that has been chromated, and baked at 160 ° C. for 30 minutes. A test plate was obtained.

Comparative Examples 5 and 6: Application to Powder Coatings Clear powder coatings and enamel powder coatings were obtained in the same manner as in Examples 8 and 9, except that the charge composition was changed as shown in Table 4. It was.
Using an electrostatic powder coating machine, the above powder coating is applied to a 0.6 mm thick molten alloyed galvanized steel sheet that has been chromated, and baked at 160 ° C. for 30 minutes. A test plate was obtained.

Using the test plate prepared by the above method, performance evaluation was performed by the following test method.
(1) Appearance of coating film Occurrence of pinholes due to foaming or the like in the coating film and distortion when a fluorescent lamp was copied onto the coating film were visually determined to confirm the smoothness and sharpness of the coating film.
(2) Impact resistance Using an impact deformation tester [JIS K-5400 (1979) 613.3 B method], a test piece is placed in a shooting mold having a radius of 6.35 mm, and a 500 g weight is dropped from a height of 40 cm. The damage of the cured film at the time of making was judged visually.
(3) Knoop hardness It measured at 20 degreeC with the M-type micro hardness meter by Shimadzu Corporation. The larger the value, the harder it is.
(4) Solvent resistance The test piece was rubbed strongly with gauze moistened with mixed xylene (JIS K 2435 product), and the surface of the test piece after 10 reciprocations was visually judged.
(5) Weather resistance Using a sunshine weather meter (JIS B-7753), the coating state was visually determined after 1000 hours exposure.
(6) Blocking resistance Each of the clear powder paint and the enamel powder paint having the composition shown in Table 4 was hermetically stored for 30 days, and the state after 10 days was visually observed.
These results are shown in Table 4.

The components and abbreviations in Table 4 indicate the following.
* 1) Epoxy group-containing acrylic resin, Fine Nippon A-247S (trade name) manufactured by Dainippon Ink and Chemicals, epoxy equivalent 630 g / mol, resin softening point temperature 109 ° C.
* 2) Bisphenol A type epoxy resin, Japan Epoxy Resin Co., Ltd. Epicoat 1002 (trade name), epoxy equivalent 650 g / mol, resin softening point temperature 78 ° C.
* 3) Acrylic fluidity modifier, Resimix L (trade name) manufactured by Mitsui Chemicals,
* 4) Rutile-type titanium oxide, DuPont's Taipure R-960 (trade name), average particle size of 35 μm,

From the results of Examples 4 to 7, the polyhemiacetal ester resin of the present invention can be applied to a thermosetting composition like the conventional polyhemiacetal ester resin.
Moreover, it turns out that the thermosetting composition using the resin is excellent in storage stability and gives a uniform and transparent cured product.
Furthermore, from Examples 8 and 9, since the resin contained a rosin skeleton in the molecule, the melt viscosity was low, the coating film was very smooth, and the cured film characteristics were also good. Furthermore, it was confirmed that each of the obtained powder coating compositions had no storage or the like and had excellent storage stability.
On the other hand, it was confirmed that each powder coating composition using a conventional polyhemiacetal ester resin has poor smoothness of the coating film, and further, blocking occurs and there is a problem in storage stability.

1A is an infrared absorption spectrum chart of rosin alcohol. FIG. 1B is an infrared absorption spectrum chart of hydrogenated trimellitic anhydride. C of FIG. 1 is an infrared absorption spectrum chart of a half esterified product of rosin alcohol and hydrogenated trimellitic anhydride. 1D is an infrared absorption spectrum chart of the polyhemiacetal ester resin obtained in Example 1. FIG. FIG. 2 is a ¹³ C-NMR chart of a half esterified product of rosin alcohol and hydrogenated trimellitic anhydride. FIG. 3 is a ¹³ C-NMR chart of the polyhemiacetal ester resin obtained in Example 1.

Claims (8)

  Divinyl is used for ring-opening half esterified products of rosin alcohols and compounds having one cyclic acid anhydride group and one carboxyl group in one molecule, or compounds having two cyclic acid anhydride groups in one molecule. A polyhemiacetal ester resin having a weight average molecular weight of 1,000 to 1,000,000 obtained by addition reaction of a (thio) ether compound. The polyhemiacetal ester resin according to claim 1, which has a group represented by the following formula (1) or (2) as a repeating unit, and the number of the repeating unit is 2 to 500.

[Wherein R ¹ is a trivalent organic group having 1 to 50 carbon atoms, R ² is a divalent organic group having 1 to 50 carbon atoms, Y ¹ is an oxygen atom or a sulfur atom, ¹ represents a residue of rosin alcohol. ]

[Wherein R ³ is a tetravalent organic group having 1 to 80 carbon atoms, R ⁴ is a divalent organic group having 1 to 50 carbon atoms, Y ² is an oxygen atom or a sulfur atom, and ² represents a residue of rosin alcohol. ] 3. The method for producing a polyhemiacetal ester resin according to claim 1 or 2, wherein the following step I and step II are performed.
Step I: Half-esterification of a compound having one cyclic acid anhydride group and one carboxyl group in one molecule or a compound having two acid anhydride groups in one molecule on the alcoholic hydroxyl group of rosin alcohol Process.
Step II: Further, a step of adding a divinyl (thio) ether compound to the generated carboxyl group.   The method for producing a polyhemiacetal ester resin according to claim 3, wherein a base catalyst is used as a catalyst in the reaction of the step I. A component; the polyhemiacetal ester resin according to claim 1 or 2,
B component; The thermosetting composition characterized by containing the compound which has 2 or more of the reactive functional groups which can form a chemical bond with a carboxyl group in 1 molecule.   Furthermore, C component; The thermosetting composition of Claim 5 formed by containing an acid catalyst.   The thermosetting composition according to claim 5 or 6, wherein the acid catalyst of component C is a heat latent acid catalyst that exhibits activity during heat curing.   A cured resin product obtained by curing the thermosetting composition according to any one of claims 5 to 7.

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