JPS63150313A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can give a cured product excellent in heat resistance, weathering resistance, and water resistance, by mixing a specified polyether compound with a polymerizable double bond-containing compound and a radical polymerization initiator. CONSTITUTION:A curable resin composition formed by mixing a polyether compound of formula I with a polymerizable double bond-containing compound and a radical polymerization initiator. In the formulas, R is an organic compound residue containing l active hydrogens, n1, n2...nl are each 0 or 1-100, and their sum is 1-100, l is the functionality of R and is 1-100 and A represents formula II. The polyether compound can be obtained by reacting an active hydrogen compound with 4-vinylcyclohexene 1-oxide in the presence of a catalyst. Said radical polymerization initiators are benzoyl peroxide, t-butyl benzoate, etc. which are usually used for unsaturated polyester resins.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermosetting resin composition that provides a cured product with excellent heat resistance, weather resistance, and water resistance.

More specifically, the present invention relates to a radically polymerizable thermosetting resin composition that can be widely used as paints, adhesives, molding materials, and the like.

[Prior Art] Unsaturated polyester resin is a typical thermosetting resin that utilizes radical polymerization.

The main raw materials for unsaturated polyester resins are broadly classified into glycols, unsaturated dibasic acids, saturated dibasic acids, and polymerizable monomers that participate in polymerization as crosslinking agents. There are many types of resins, and depending on their combinations and blending ratios, resins with various □performances can be obtained.

In addition, it has excellent curability, no volatile 01 organisms during curing, and can be molded under low pressure, making it excellent in practical terms.

House-like vessels and construction equipment take advantage of these features.

Various molding materials such as civil engineering materials, decorative supplies, electrical parts, etc.
Widely used in paints, adhesives, etc.

However, it lacks weather resistance, has poor hydrolysis resistance because it contains ester bonds, and is electrically insulating.

It also has various drawbacks, such as a lack of heat resistance.

On the other hand, diallyl phthalate resin is an example of a radically polymerizable resin having excellent electrical properties and water resistance.

These are used for electrical insulation boards, decorative boards, etc.
Its range of use is limited because it is hard, brittle, and lacks adhesive properties.

Furthermore, diethylene glycol bisallyl carbonate is used as a transparent plastic material, but it has drawbacks in molding methods, adhesive properties, etc.

[Problems to be Solved by the Invention] In view of the above circumstances, as a result of intensive studies by the present inventors, a vinyl compound proposed in JP-A-60-161940 (title of invention: polyether compound) A polyether compound with double bonds has radical polymerizability, and its cured product is heat resistant and weather resistant.

We have completed the present invention by discovering a scale that has excellent flexibility and compensates for the drawbacks of unsaturated polyester resins and diallyl phthalate resins as described above.

[Structure of the invention] That is, the present invention (a) Polyether compound represented by general formula (I) (b) Compound having a polymerizable double bond (C) Radical initiator A curable resin composition containing However, R is an organic compound residue having one active hydrogen.

nl, n2... nl is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100.

1 is an integer from 1 to 100 and represents the functional number of R.

A is expressed by the following formula.

Next, the present invention will be explained in detail.

(I) which is the main resin component of the curable resin composition of the present invention
In the polyether compound represented by the formula, the organic residue having active hydrogen is introduced from the compound represented by R-(H), (H represents an active hydrogen group) (an integer from 1-1 to 100). Indicates a substituent.

Specific examples of organic substances having active hydrogen include alcohols, phenols, carboxylic acids, amines, and thiols.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

For example, aliphatic alcohols such as methanol, ethanol, n-propertool, iso-propertool, n-butanol, iso-butanol, pentanol, hexanol, octatool, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1.3
Butanediol, 1.4-butanediol, betanediol, 1,6-hexanediol, neopentyl glycol, oxypivalic acid neobentyl glycol ester, cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, Examples include polyhydric alcohols such as methylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S1 phenolic resin, Talesol novolak resin, and the like.

Carboxylic acids include formic acid, acetic acid, propionic acid, acetic acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane 2'Fi, trimellitic I acid, pyromellitic acid, polyacrylic acid, phthalic acid, and isophthalic acid. , terephthalic acid, etc. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Examples of amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4°-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, and xylene. Examples include diamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

Examples of thiols include mercapto compounds such as methyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol esters of mercaptopropionic acid, such as ethylene glycol dimercaptopropionic acid ester, and trimethylolpropane trimercaptopropionic acid. , pentaerythritol, pentamerkabutobro, and onic acid.

In addition, other active hydrogen-containing compounds include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, cellulose resins such as hydroxyethyl cellulose, acrylic polyol resins, and styrene allyl alcohol copolymers. Examples include resins, styrene-maleic acid copolymer resins, alkyd resins, polyester polyol resins, polyester carboxylic resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycols, and polybutadiene having ○HW.

In addition, any compound having active hydrogen can be used, and two or more of them may be used in combination.

In the present invention, nl, n2, n3...nu are 0 or an integer from 1 to 100. The sum is 1 to 100, and 10
If it is above 0, it becomes a solid with a high melting point.

In reality, it is not something that can be used.

p is an integer from 1 to 100. It is an integer represented by the functional number of R.

The polyether compound in the present invention can be obtained by reacting the above-mentioned active hydrogen-containing compound with 4-vinyl-cyclohexene-1-oxide in the presence of a catalyst.

By changing the reaction ratio of 4-gonyl-cyclohexene-1-oxide (formula below) and the active hydrogen compound, n
1,n2,n3---nfI to obtain vinyl compounds (1) containing up to 100 ether groups.

In practice, the above compound is a mixture of compounds represented by general formula (1).

It is preferable to use a catalyst when polymerizing in the presence of these active hydrogens.

Catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine, organic basic acids such as pyridines and imidazoles, organic acids such as formic acid, acetic acid, and propionic acid, Ia acids, and hydrochloric acid. ! , alkali metal alcoholades such as sodium methylate, KOH, N
Alkali such as aOH, BF, ZnCj 1 A
Examples include Lewis acids such as lCl2 and SnCN4 or their complexes, and organometallic compounds such as triethylaluminum and diethylzinc.

These catalysts can be used in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the starting material.

The reaction temperature is -20 to 200°C, preferably 0°C to 120°C.
“It is C.

The reaction can also be carried out using a solvent.

A solvent containing active hydrogen cannot be used.

That is, ethyl acetate9. Esters such as ethyl propionate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons such as chloroform and carbon tetrachloride; dimethyl formamide and dimethyl sulfonate. It is also possible to react in the presence of oxides, etc.

Examples of compounds having double bonds in the present invention include styrene, vinyltoluene, and chlorostyrene.

Compounds with styrenic double bonds such as divinylbenzene: acrylic esters such as methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate; methacrylic esters; diallylphthalate and its polymers (prepolymers); ), vinyl ethers such as ethyl vinyl ether and butyl vinyl ether, allyl compounds such as diethylene glycol bisallyl carbonate and its polymers, unsaturated dicarboxylic acids such as phthalic anhydride, fumaric acid, and phthalic acid, and phthalic anhydride. maleimides such as N-phenylmaleimide, N,N"-phenylenebismaleimide, N,N"-methylene-〇-phenylenebismaleimide derived from , and unsaturated polyester resins derived from phthalic anhydride. .

These can be used alone or in combination to further enhance the properties.

Although the compound represented by formula (1) and the compound having a double bond can be mixed in any ratio depending on the purpose, 5/95 is usually used to take advantage of the characteristics of the compound represented by formula (1).
: It is preferable to mix at a ratio of 95 to 5.6 Radical initiators in the present invention include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, which are usually used for unsaturated polyester resins.
Such as t-butylcumyl peroxide.

These can be used alone or in combination of two or more.

A curing agent can also be used in combination to accelerate curing.

As a curing accelerator, cobalt naphthenate, cobalt octoenoate, manganese naphthenate, dimethylaniline, N
, N-diethylaniline, N,N-dimethylpara-toluidine, pyridine, phenylmorpholine, and the like can be used.

The radical initiator is used in an amount of 0.1 to 5%, preferably 0.5 to 3%, based on the total weight of the polyether compound and the compound having a polymerizable double bond.

If it is less than 0.1%, sufficient curing speed cannot be obtained,
Moreover, if it exceeds 5%, the cured product may become brittle.

It can also cause foaming.

The composition of the present invention may optionally contain glass fibers, potassium titanate II fibers, gold sole fibers, and ceramic fibers.

Calcium carbonate, silica, carbon black, metal powder,
Including reinforcing fillers such as asbestos and glass powder,
Dyes, pigments, mold release agents, lubricants, heat stabilizers, antioxidants, UV absorbers, foaming agents, flame retardants.

A coupling agent etc. can be used together.

It can also be used as a paint by diluting it with a solvent.

[Effect of the invention] The composition of the present invention has excellent weather resistance and transparency.

Due to its good heat resistance and hydrolysis resistance, it has great industrial utility, and is used as electrical and electronic parts, as well as mechanical parts.

Production of automobile parts, building material parts, etc. It can be used for shapes, paints, adhesives, etc.

Claims (1)

[Scope of Claims] (a) A polyether compound represented by general formula (I) (b) A compound having a polymerizable double bond (c) A curable resin composition containing a radical initiator ▲Math. There are chemical formulas, tables, etc. ▼ (I) However, R is an organic compound residue with 1 active hydrogens. n1, n2...nl is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100. l is an integer from 1 to 100 and represents the functional number of R. A is expressed by the following formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼