JPH02178319A - Thermosetting composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of satisfying storage stability and mechanical properties and further controlling curing starting temperature by blending a polyol with a monomer having a cationic polymerizable functional group using a specific pyridinium or sulfonium salt. CONSTITUTION:The objective composition obtained by blending (A) a monomer (e.g. epoxide, cyclic imino or cyclic ether) having a cationic polymerizable functional group, polymer or a mixture thereof with (B) 0.01-1wt.% (based on solid substances in the composition) pyridinium or sulfonium salt expressed by formula I or II (R1 to R4 are H, halogen, alkyl, alkoxy, nitro, amino, hydroxy, cyano, carbamoyl or alkanoyl; M is As, Sb, B or P; X is halogen; n is 4 when M is B and 6 in the other cases) and (C) 1-100mol% (based on cationic polymerizable functional group) polyol (e.g. caprolactone polyol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cationically polymerizable thermosetting compositions useful as vehicles for paints, adhesives, printing inks, and the like.

A thermosetting resin composition prepared by blending a sulfonium salt as a thermally cleavable cationic polymerization initiator with a resin having a cationically polymerizable cyclic functional group, such as an epoxy resin, has been disclosed in JP-A-58-37003, Intermediate 58. -37004.

Recently, the present inventors have disclosed a similar thermosetting resin composition containing a pyridinium salt as a cationic polymerization initiator. See patent application No. 63-131171.

The cationic polymerization initiators used in these compositions are thermally cleaved to produce carbonium cations and initiate polymerization, so when used as a curing agent for liquid epoxy resin, for example, they do not react at room temperature and The polymerization reaction starts at a high temperature such as above .degree. C., so that a liquid-type epoxy resin composition with a long pot life and excellent storage stability can be obtained.

The curing initiation temperature and curing rate of these thermosetting compositions are controlled by the molecular structure of the cationic polymerization initiator used, and in order to obtain curing compositions with different curing initiation temperatures or curing reaction rates, it is necessary to select an initiator suitable for the curing composition. I had to choose and use it.

SUMMARY OF THE INVENTION The present invention relates to a thermosetting composition comprising a monomer or polymer having a cationically polymerizable functional group, or a mixture thereof, and a cationic polymerization initiator.

According to the invention, the thermosetting composition further comprises a polyol, and the cationic polymerization initiator is selected from a pyridinium salt of the formula or a sulfonium salt of the formula.

In the formula, R1, R2, R3 and R4 are hydrogen, halogen,
alkyl, alkoxy, nitro, amino, hydroxy,
Cyano, alkoxycarbonyl, carbamoyl or alkanoyl.

h is As, Sb, B or P.

X is halogen.

n is 4 when h is B, and 6 otherwise.

Preferably, the cationically polymerizable functional group is an epoxide group, a cyclic imino group, a cyclic ether group, or a vinyl group, and the polyol is blended in an amount of 1-100 mol % based on the cyclic functional group.

The cationic polymerization initiator can preferably be blended in an amount of 0.01 to 10% by weight based on the solid content of the composition.

By blending the polyol into the composition of the present invention, it reacts with the cationically polymerizable functional group and is incorporated into the polymer.
Copolymerize. This accelerates the curing rate, and as a result, the curing initiation temperature can be controlled while satisfying the storage stability of the curable composition containing the thermally cleavable cationic polymerization initiator and the mechanical properties of the polymer.

Examples of monomers having a cationically polymerizable functional group include epoxides, cyclic imines, cyclic ethers, and vinyl.

In addition, in order to use the composition as a vehicle for paints, adhesives, printing inks, etc., oligomers/polymers that can be polymerized in a liquid state at the current temperature before curing can also be used. It must have the same structure as the cationically polymerizable monomer.

The composition may be of a hot solvent type using the low-viscosity polyol and/or cationically polymerizable monomer as a reactive diluent, but may also contain a solvent to adjust the viscosity during coating.

A typical example of a cationically polymerizable curable resin is an epoxy resin. Examples include bisphenol epoxy resins and novolac type epoxy resins such as bisphenol A, bisphenol S1 and bisphenol F, diglycidyl ethers of glycols such as butanediol, hexanediol, and hydrogenated bisphenol A; polyethylene glycol, polypropylene glycol Diglycidyl ethers of polyoxyalkylene glycols such as , polybutylene glycol, and adducts of bisphenol and alkylene oxide; diglycidyl esters of dicarboxylic acids such as terephthalic acid, isophthalic acid, fucuric acid, and adipic acid; Examples include glycidyl ether esters of hydroxycarboxylic acids such as hydroxybenzoic acid.

Another preferred example of the cationically polymerizable resin component is an acrylic resin containing an epoxide group.

This includes glycidyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate.
(Meth)acrylic acid esters such as isobutyl acrylate, 2-ethylhexyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; other monomers such as styrene and its derivatives, (meth)acrylonitrile, vinyl acetate, etc. It can be obtained by copolymerizing these by a conventional method.

As the polyol, low molecular weight polyols such as ethylene glycol, propylene glycol, tetramethylene glycol, diethlene glycol, glycerin, trimethylpropane, and pentaerythritol can be used. 1 (1 causes new polymerization of cationically polymerizable functional groups, resulting in a decrease in the average molecular weight and mechanical properties of the polymer, so polyether polyols, polyester polyols, caprolactone polyols, acrylic polyols) More preferred are oligomeric polyols such as.

These polyols are blended in an amount of 1 to 100 mol%, preferably 5 to 50 mol%, based on the cationically polymerizable functional group. If the blending amount is too small, the effect of adjusting the curing start temperature will not be exhibited, and high solids cannot be achieved, and if the blending amount is too small, the curability will decrease.

The composition of the present invention contains the initiator in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the solid content of the resin component.
include. If the amount of the initiator is too small, the curability will be reduced, and if it is used in excess, the appearance and physical properties will be adversely affected, such as coloration of the cured product and a decrease in water resistance.

The composition may contain additives such as pigments and fillers depending on its use.

The composition of the present invention can be of a high solid or solvent-free type, has excellent storage stability at room temperature, and is cured by starting a cationic polymerization reaction by cleavage of the initiator at the curing temperature. In this case, the curing initiation temperature can be adjusted lower and/or the curing reaction rate can be accelerated compared to a composition that does not contain a polyol. The curing time depends on the temperature, but is generally within 1 hour.

The invention will now be illustrated by examples. “Part” in Examples
and "%" by weight.

Reference Example Synthesis of Polymer A Polymer A was obtained by polymerizing acrylic monomers and a radical polymerization initiator in the following formulation by a conventional method.

(Polymerization temperature: 120°C) Characteristics of the obtained polymer: NV = 60.5 parts Viscosity = M-
N Molecular weight = 3500 Example 1 pt-butylbenzyl P for 00 parts of polymer Al
-cyanopyridinium hexafluoroantimonate 0
．． 5 parts and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel Corporation).

2.95 parts (7 mo1%) of molecular weight 860 was added and applied on a tin plate by flow coating. After baking this coated slope at 130° C. and 150° C. for 30 minutes, the curing properties were examined by touch with the fingers, and the results are shown in Table 1 below along with the viscosity of the mixture.

Example 2 pt-butylhensyl P for 100 parts of polymer A
-cyanopyridinium hexafluoroantimonate 0
．． 5 parts and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel Corporation).

Add 5.90 parts (14 mo1%) of molecular weight 860,
It was applied on a tin plate using a flow coat. This painted board is heated to 130℃
After baking at 150° C. and 150° C. for 30 minutes, the curing properties were examined by touch, and the results are shown in Table 1 below along with the viscosity of the mixture.

Example 3 pt-butylbenzyl P per 00 parts of polymer Al
-cyanoviridinium hexafluoroantimonate 0
．． 5 parts and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel Corporation).

Molecule 1a6ozx, so part (28mol1%) was added and applied on a tin plate by flow coating. This coating was baked at 130℃ and 150''C for 30 minutes each, and the hardness was determined by finger touch.
The results were shown in

Example 4 pt-butylbenzyl P- to 100 parts of polymer A
Cyanoviridinium hexafluoroantimone 1-0
．． 5 parts and Plaxel 3o8 (trifunctional polycaprolactone polyol manufactured by Daicel, molecule 1860) 29.5
(70 mo1%) and applied it on a tin plate by flow coating. After baking this coated plate at 130°C and 150'C for 30 minutes, the curing properties were examined by touch, and the results are shown in Table 1 below along with the viscosity of the mixture.

Comparative Example 1 pt-butylbenzyl P per 100 parts of polymer A
-cyanopyridinium hexafluoroantimone h
5 parts of O. was added and applied by flow coating onto a tin plate. After baking the coated plates at 130'c and 160'c for 30 minutes, the curing properties were examined by touch and the results are shown in Table 1 below along with the viscosity of the mixture.

Table 1 Viscosity of mixture and curability at each baking temperature Example 5 2.4 dichlorohensyl 4 per 100 parts of polymer A
-cyanoviridinium hexafluoroantimonate 0
．． 5 parts and polyether polyol (trifunctional 1 molecular weight 8
00) and applied it on a tin plate by flow coating. This painted board was heated to 130°C and 150°C for 30
After baking, the curing properties were examined by touch with the fingers, and the results are shown in Table 2 below along with the viscosity of the mixture.

Example 6 0.5 part of 2,4 dichloro-, 4-cyanobili Jium hexafluoroantimonomer and 5.90 parts of polyether polyol (trifunctional monomolecular weight 800) (14 mo 1%) per 100 parts of polymer A ) was added and applied on a tin plate by flow coating. This coated board was heated to 130℃ and 15℃.
After baking at 0° C. for 30 minutes, the curing properties were examined by touch with the fingers, and the results are shown in Table 2 below along with the viscosity of the mixture.

Example 7 2,4 dichlorohensyl 4 to 100 parts of polymer A
-cyanoviridinium hexafluoroantimobutyrate 0
．． 5 parts and polyether polyol (trifunctional 1 molecular weight 8
00) was added and applied by flow coating onto a tin plate. This coated board was heated to 130℃ and 15℃.
After baking at 0° C. for 30 minutes, the curing properties were examined by touch with the fingers, and the results are shown in Table 2 below along with the viscosity of the mixture.

Example 8 4 parts of 2,4 dichlorobenzyl per 100 parts of polymer A
-cyanoviridinium hexafluoroantimonate 0
．． 5 parts and polyether polyol (trifunctional 1 molecular weight 8
00) 29.5 parts (70 mo1%) was added and applied on a tin plate by flow coating. This painted plate was heated to 130℃ and 150℃.
After baking at ℃ for 30 minutes, the curing properties were examined by finger touch, and the results are shown in Table 2 below along with the viscosity of the mixture.

Comparative Example 2 4 parts of 2,4 dichlorobenzyl per 100 parts of polymer A
-cyanoviridinium hexafluoroantimonate 0
．． 5 parts were added and applied by flow coating onto a tin plate. After baking the coated plates at 130° C. and 160° C. for 30 minutes, the curing properties were examined by touch with the fingers, and the results are shown in Table 2 below along with the viscosity of the mixture.

(Space below) Table 2 Viscosity of mixture and curability at each baking temperature Example 9 0 p-chlorohenzyltetrahydrothiophenium hexafluoroantimonate per 100 parts of polymer A
．． 5 parts and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel Corporation).

Add 2.95 parts (7 mo1%) of molecule ff1860,
It was applied on a tin plate using a flow coat. This painted board is heated to 130℃
After baking for 30 minutes at 150° C. and 150° C., the curing properties were examined by touch, and the results are shown in Table 3 below along with the viscosity of the mixture.

Example IO 0 p-chloropenzyltetrahydrothiophenium hexafluoroantimonate per 100 parts of polymer A
．． 5 parts and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel Corporation).

5.90 parts (14 mo1%) of molecular weight 860 were added and applied on a tin plate by flow coating. After baking the coated plates at 130° C. and 150° C. for 30 minutes, the curing properties were examined by finger touch, and the results are shown in Table 3 below along with the viscosity of the mixture.

Example 11 0.5 parts of p-chlorobutylbenzyltetrahydrothiophenium hexafluoroantimonate and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel, molecular weight 860) 11 based on 100 parts of polymer A
．． 80 parts (28 mo1%) was added and applied on a tin plate by flow coating. After baking this coated plate at 130°C and 150°C for 30 minutes, the curing properties were examined by touch.
The results are shown in Table 3 below along with the viscosity of the mixture.

Example 12 0 p-chloropenzyltetrahydrothiophenium hexafluoroantimonate per 100 parts of polymer A
．． 5 parts and Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel Corporation).

Molecule ft860) 29.5-parts (70 mo1%) were added and applied by flow coating onto a tin plate. This painted board is 13
After baking at 0° C. and 150° C. for 30 minutes, the curing properties were examined by touch with the fingers, and the results are shown in Table 3 below along with the viscosity of the mixture.

Comparative Example 3 0 parts of p-chlorobenzyltetrahydrothiophenium hexafluoroantimonate per 00 parts of polymer Al
．． 5 parts were added and applied to a yellowtail medium plate by flowing coating. After baking the coated plates at 130"C and 160"C for 30 minutes, the curing properties were examined by finger touch, and the results are shown in Table 3 below along with the viscosity of the mixture.

(Margin below)

Claims (5)

[Claims] (1) A thermosetting composition comprising a monomer or polymer having a cationically polymerizable functional group, or a mixture thereof, and a cationic polymerization initiator, wherein the composition further comprises a polyol, and the cationic polymerization initiator has the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3 and R_4 are hydrogen,
halogen, alkyl, alkoxy, nitro, amino or hydroxy, cyano, carbamoyl or alkanoyl, M is As, Sb, B or P, X is halogen, n is 4 when M is B; , otherwise 6. ) A thermosetting composition characterized in that it is a pyridinium salt or a sulfonium salt. (2) The thermosetting composition according to item 1, wherein the functional group is an epoxide group, a cyclic imino group, a cyclic ether group, or a vinyl group. (3) The thermosetting composition according to item 1 or 2, wherein the polyol is caprolactone polyol, polyether polyol, polyester polyol, or acrylic polyol. (4) The thermosetting composition according to any one of Items 1 to 3, wherein the polyol is blended in an amount of 1 to 100 mol % based on the cationically polymerizable functional group. (5) The thermosetting composition according to any one of Items 1 to 4, wherein the cationic polymerization initiator is blended in an amount of 0.01 to 10% by weight based on the solid content of the composition.