JPH0780995B2 - Epoxy resin jig - Google Patents

Description

TECHNICAL FIELD The present invention relates to a jig and tool made of an epoxy resin.

More specifically, it relates to an epoxy resin jig having excellent heat resistance and electrical characteristics.

<< Prior Art >> Plastic tooling is a tool developed and developed mainly in the US aircraft and automobile industries. In the early stages of development, resins such as phenol and polyester were used, but the characteristics as a jig and tool material are difficult, and the results are not necessarily satisfactory.It is an exaggeration to say that it was put into practical use by registering epoxy resin. Absent. Twenty years ago, plastic jigs and tools were introduced to Japan by a person involved in epoxy resin, and they grew in step with the rapid development of the automobile industry, and it is believed that they have now established solid citizenship in the jigs and tools field. To be

Especially in the automobile industry, where it is necessary to prepare a large amount of jigs and tools in a short time for frequent model changes, and in the aerospace industry that requires various kinds of jigs and tools, the industry is in full-scale use. It greatly contributes to shortening delivery times and reducing costs.

The purpose of the resin jig is to solve the disadvantages of metal by using a resin, and the following are the advantages of the epoxy resin jig compared to the steel jig.

(1) The production cost should be reduced.

(2) Easy production, that is, the production period can be shortened.

(3) The weight of jigs and tools can be reduced. Epoxy laminated products are about one-fourth of steel and about three-fifths of aluminum, which has great effects such as reducing operator fatigue and easiness of transportation.

(4) It is possible to easily build up the wear of jigs and tools, and to correct it by changing the design.

(5) Generally, storage is easy and maintenance costs are low.

However, the epoxy resin, which is an organic material, is considerably inferior to the metal material in terms of thermal characteristics.
It is a headache for people involved in plastic tools as well as strength problems. The heat resistance value of resin varies depending on the type of resin and curing agent, curing conditions, exposure time load stress, etc., and room temperature curing type resin is 60 ° C to 80 ° C, and heat curing type resin is 120 ° C to 250 ° C. Being developed. However, there are problems in jig manufacturing technology, and its use is extremely difficult.

<Problems to be Solved by the Invention> In view of these circumstances, the present inventors diligently studied, and
It has been found that an epoxy resin jig having excellent heat resistance and moldability can be obtained by using the epoxy resin having a doxycyclohexane skeleton proposed in JP-A-60-166675, and the present invention has been completed.

<< Means for Solving the Problems >> That is, the present invention provides "(a) the following general formula (I)" [However, R ¹ is an organic compound residue having ¹ active hydrogen, and the organic compound is one kind selected from a saturated hydroxyl group-containing compound having a valence of 1 or more or a hydroxyl group-containing compound having an unsaturated double bond. Or a mixture of two or more kinds, n ₁ , n ₂ , ...
... n1 is 0 or an integer of 1 to 30 and the sum thereof is 1 to
100, 1 is an integer of 1 to 10 and represents the number of functional groups of R ¹ , A is an oxycyclohexane skeleton having a substituent X, and is represented by the following formula: R ² is any one of H, an alkyl group, an alkylcarbonyl group and an arylcarbonyl group, Is one or more contained in the resin represented by the formula (I)] [Epoxy resin jig (b) Epoxy resin jig comprising a curing agent for epoxy resin].

Hereinafter, the present invention will be described in detail.

In the epoxy resin represented by the general formula (I), which is the main component of the epoxy resin jig of the present invention, R ¹ is a residue of a saturated alcohol which is an organic compound having active hydrogen. The saturated alcohols may be monohydric alcohols or polyhydric alcohols.
For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol and other aliphatic alcohols, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1,3 butanediol, 1,4 butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol oxypivalate, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, tri Methylolethane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bifphenol S, polyvinyl alcohol, polyvinyl acetate hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxy Ethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, polyester polyol resin, polycaprolactone polyol resin, polypropylene There is a polyhydric alcohol such as polyol polytetramethylene glycol.

The hydroxyl group-containing compound may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, 3-cyclohexenemethanol, hydroxyalkyl (meth) acrylate and the like. Any compound can be used as long as it has the above-mentioned active hydrogen, and two or more kinds thereof may be mixed.

N ₁ , n ₂ , ..., N ₁ in the general formula (I) are each 0
Alternatively, the sum is an integer of 1 to 30 and is 1 to 100. l is the number of hydroxyl groups of the initiator, and is an integer of 1 to 10. n ₁ ,
n _2, becomes high melting point resin is a sum of · · · · n1 is 100 or more, difficult to handle in practice does not become like can be used.

A in the general formula (I) is an oxycyclohexane skeleton having a substituent X and is represented by the following formula: R ² is any one of H, an alkyl group, an alkylcarbonyl group and an arylcarbonyl group, Is essential to be contained in the resin represented by the formula (I) in an amount of 1 or more, and the more, the better.

Is preferably as small as possible.

That is, in the epoxy resin which is the main product of the epoxy resin jig of the present invention, the substituent X is Is the main one.

A jig and tool made of the epoxy resin of the present invention comprises (I)
The epoxy resin represented by the formula is produced by using the above-mentioned hydroxyl group-containing organic compound as an initiator and 4-vinylcycloxene-
Polyether resin obtained by ring-opening polymerization of 1-oxide, that is, produced by epoxidizing vinyl group side chain of polycyclohexene oxide polymer having vinyl group side chain with oxidizing agent such as peracid You can

4-Vinylcycloxene-1-oxide can be obtained by partially epoxidizing 4-vinylcyclohexene obtained by the dimerization reaction of ptadiene with peracetic acid or the like.

It is preferable to use a catalyst when polymerizing 4-vinylcycloxene-1-oxide in the presence of active hydrogen.

As the catalyst, amines such as methylamine, ethylamine, propylamine and piperazine, organic bases such as pyridine and imidazole, organic acids such as formic acid, acetic acid and propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, sodium methylate and the like. Calcal metal alcoholates, alkalis such as KOH and NaOH, Lewis acids such as BF ₃ , ZnCl ₂ , AlCl ₃ and SnCl ₄ or their complexes, triethylaluminum, and organometallic compounds such as diethylzinc. it can.

These catalysts can be used in the range of 0.01 to 10%, preferably 0.1 to 5% with respect to the starting material.

The reaction temperature is -70 to 200 ° C, preferably -30 ° C to 100 ° C.

The reaction can also be carried out using a solvent.

A solvent having active hydrogen cannot be used as the solvent.

That is, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters and the like can be used.

The polycyclohexene oxide polymer having a vinyl group side chain thus synthesized is epoxidized with an epoxidizing agent to produce the epoxy resin of the formula (I) according to the present invention.

As the epoxidizing agent, peracids and hydroperoxides can be used.

As the peracids, formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like can be used.

Of these, peracetic acid is a preferable epoxidizing agent because it is industrially available at low cost and has high stability.

As the hydroperoxides, hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like can be used. A catalyst may be used in the epoxidation, if necessary.

For example, in the case of peracid, an acid such as alkali of sodium carbonate or sulfuric acid can be used as a catalyst.

In the case of hydroperoxide, a catalyst effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide or an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. it can.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials.

Depending on the conditions of the epoxidation reaction, the epoxidation of the olefin bond and at the same time the epoxide group And generated substituents As a result of reacting with the epoxidizing agent, a modified substituent is generated and contained in the target compound. The ratio of the three types of auxin groups in the target compound depends on the type of epoxidizing agent, the molar ratio of epoxidizing agent olefin bond, and the reaction conditions.

When the epoxidizing agent is peracetic acid, the modified substituent mainly has a structure as shown below and is generated from the generated epoxy group and by-product acetic acid.

The target compound is obtained by usual scientific engineering means such as concentration.
It can be taken out from the reaction crude liquid.

The curing agent used for the epoxy resin, which is the main component of the jig of the present invention, may be the curing agent used for Kochi's epoxy resin, such as amines, polyamide resin, polymercaptan resin, novolac resin, dicyandiamide, and trifluoride. Included are boron fluoride amine complexes.

Here, the amines include the following.

Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, mensendiamine, metaxylenediamine, bis (4-amino-3-methylcyclohexyl) methane, and adducts of the aliphatic polyamines with known epoxy compounds, and reaction products with acrylonitrile. , A reaction product with a ketone, an adduct of a known epoxy compound with an aromatic polyamine such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfide,
Secondary and tertiary amines such as tris (dimethyldiaminomethyl) phenol, piperidine, imidazole and its derivatives, and salts thereof.

The polyamide resin includes a reaction product of a fatty acid such as fatty acid, dimer acid and trimer acid with an aliphatic polyamine.

The acid anhydride includes the following.

Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride Acid anhydrides such as succinic anhydride and dodecenyl succinic anhydride, and mixtures of the above acid anhydrides.

Novolac resins include low molecular weight resinous products obtained by condensation of phenol or a mixture of phenol and cresol, dihydroxybenzene and formaldehyde.

The amine complex of boron trifluoride is an amine complex of boron trifluoride with a low molecular weight amine compound such as monoethylamine, piperidine, aniline, butylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, tributylamine, triethanolamine. Is included.

Further, as other curing agents, there are diazonium salts, iodonium salts, bromonium salts, sulfinium salts of super strong acids such as boron tetrafluoride, phosphorus hexafluoride and arsenic hexafluoride. Further, among these curing agents, aliphatic polyamines, aromatic polyamines, polyamide resins, polymercaptan resins can be mixed and used at any ratio,
A curing accelerator may be used alone or in combination for the purpose of adjusting the curing rate. Here, the secondary and tertiary amines can be used as the curing accelerator.

The acid anhydride may be used as it is, but a curing catalyst and a curing accelerator may be used in combination for the purpose of adjusting the curing rate and improving the physical properties of the cured product. Here, the second and third amines and tin octylate are used as the curing catalyst, and water, alcohols such as methanol, ethanol, propanol, isopropanol, cyclohexanol and ethylene glycol, acetic acid, etc. as the curing accelerator. They are carboxylic acids such as propionic acid, succinic acid and hexahydrophthalic acid, and amines having active hydrogen such as ethylenediamine and diethylenetriamine.

The novolac resin may be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalyst is the secondary and tertiary amines.

Dicyandiamide may be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalyst is the secondary and tertiary amines.

The amine complex of boron trifluoride may be used alone or in combination with a curing rate adjusting agent for the purpose of controlling the curing rate.
Here, the curing rate adjusting agent may be any as long as it can be used for conventional epoxy resins, and specifically, for example, carboxylic acids, amines, metal acetylacetones, titanium, tin and the like. Organic metal compounds, glycols, organic boron compounds and the like are included.

In the epoxy resin jig of the present invention, the general formula (I)
As long as the characteristics of the epoxy resin represented by
It can be used as a mixture with other epoxy resins.

Here, any other epoxy resin may be used as long as it is generally used, and examples thereof include epibis type epoxy, bisphenol F epoxy, and novolac epoxy resin.

Further, the present epoxy resin jig can be manufactured according to a normal jig manufacturing method.

[Effects of the Invention] The epoxy resin jig of the present invention obtained as described above has excellent heat resistance and thus can be widely used in various applications.

The present invention will be further described below with reference to examples.

Synthesis Example 1 58 g (1 mol) of allyl alcohol, 868 g (7 mol) of 4-vinylcyclohexene-1-oxide and 4.7 g of BF ₃ etherate were mixed at 60 ° C., and 4-vinylcyclohexene-1-oxide was analyzed by gas chromatography. The conversion rate of
Reacted until 98% or more.

Ethyl acetate was added to the obtained reaction crude liquid and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectrum of the product, the absorption by the epoxy group at 810, 850 cm ^-1 found in the raw material has disappeared, the absorption by the ether bond at 1080, 150 cm ^-1 is present, by gas chromatography analysis, Although the amount of allyl alcohol in the product was a trace amount, it was confirmed in the infrared absorption spectrum that the compound had a structure represented by the following formula since the OH group was absorbed at 3450 cm ^-1 .

429 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 395 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours.

During this time, the reaction temperature was kept at 40 ° C.

After the addition of peracetic acid was completed, the mixture was aged at 40 ° C. for 6 hours.

Ethyl acetate was added to the reaction crude liquid, washed with alkaline water containing 416 g of sodium carbonate, and well washed with distilled water.

The ethyl acetate layer was concentrated to give a viscous liquid.

This compound had an oxirane oxygen content of 9.27% and showed characteristic absorption due to an epoxy group at 1260 cm ^-1 in an infrared absorption spectrum.

Furthermore the absorption by the residual vinyl group to 1640 cm ^-1 is observed, further -OH group in 3400 cm ^-1, the 1730 cm ^-1 Since this compound is absorbed by the compound of the general formula (I)
(R ¹ : glycidyl group or allyl group, n = 7 on average, including a group in which 1 part of acetic acid is added to an epoxy group) was confirmed.

Synthetic Example 2 134g of trimethylolpropane was prepared in the same manner as in Synthetic Example 1.
(1 mol) of 4-vinylcyclohexene-1-oxide
1863 g (15 mol) was reacted in the same manner as in Synthesis Example 1 to obtain a product.

In the infrared absorption spectrum of the obtained product, the absorption due to the epoxy groups at 810 and 850 cm ^-1 found in the starting material was eliminated in the infrared absorption spectrum, and the absorption due to the new ether bond at 1080 and 1150 cm ^-1 Presence, and further by NMR analysis [However, n1 + n2 + n3 = 5 on average, B is an oxycyclohexane skeleton having the following vinyl groups It is confirmed that the structure is [].

The reaction of 573 g of this compound and 387 g of peracetic acid was carried out in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid.

The oxirane oxygen content of this compound was 9.03%, and characteristic absorption due to epoxy group was observed at 1260 cm ^-1 in the infrared absorption spectrum. Furthermore the absorption by the residual vinyl group to 1640 cm ^-1 is observed, further -OH group in 3400 cm ^-1, the 1730 cm ^-1 Since this compound is absorbed by the compound of the general formula (I)
Structure (R ¹ : trimethylolpropane residue, l = 3, n
1, n2, n3 = 5 on average, including 1 part of a group in which acetic acid is added to an epoxy group).

Examples 1 to 4 and Comparative Example 1 Using the epoxy resin obtained in Synthesis Example 1 and Synthesis Example 2 and Epicoat 828 manufactured by Yuka Shell Co., Ltd. as an epoxy resin with the following composition, a resin mold was formed by a casting method. The hardness and heat resistance of the resin molds prepared in were compared.

Continuation of the front page (56) Reference JP-A-60-166675 (JP, A) Hiroshi Kakiuchi "New Epoxy Resin" (Sho 60-5-10) Shokoido Co., Ltd., pp. 689, 677-692 page

Claims (1)

[Claims] (A) The following general formula (I): [However, R ¹ is an organic compound residue having ¹ active hydrogen, and the organic compound is one kind selected from a saturated hydroxyl group-containing compound having a valence of 1 or more or a hydroxyl group-containing compound having an unsaturated double bond. Or a mixture of two or more kinds, n ₁ , n ₂ , ...
... nl is 0 or an integer of 1 to 30, and the sum thereof is 1 to
100, 1 is an integer of 1 to 10 and represents the number of functional groups of R ¹ , A is an oxycyclohexane skeleton having a substituent X, and is represented by the following formula: R ² is any one of H, an alkyl group, an alkylcarbonyl group and an arylcarbonyl group, Is contained in the resin represented by the formula (I) one or more], and an epoxy resin jig and tool comprising (b) a curing agent for an epoxy resin.