JPS6272719A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a compound containing a spiroorthocarbonate group expressed by a specific formula, specific curing agent and specific curing accelerator and suitable for casting, filling, coating, bonding, etc., with almost no volume shrinkage and expansion on curing. CONSTITUTION:A composition containing (A) a curing accelerator consisting of (i) an acetylacetone complex salt based compound, e.g. acetylactone complex salt or trifluoroacetylacetone complex salt, (ii) a Lewis acid based compound, e.g. an inorganic or organic salt containing BF4<->, PF6<->, AsF6<-> and/or SbF6<-> as anion, and (iii) a metal soap based compound, (B) a compound having one or more spiroorthocarbonate groups expressed by the formula (R<1> and R<2> are bifunctional group) in the molecule and (C) a curing gent consisting of an organic polybasic acid and/or anhydride thereof. EFFECT:Lowering of curing temperature and shortening of curing time.

Description

Detailed Description of the Invention (a) Object of the Invention [Field of Industrial Application] The present invention relates to a thermosetting resin composition. The resin composition of the present invention can be used in a wide range of fields such as casting, filling, painting, adhesion, and molding.

[Conventional technology]

As thermosetting resins, epoxy resins, unsaturated polyester resins, diallyl phthalate resins, phenol resins, etc. have been used conventionally. However, these resins
Volumetric shrinkage during curing is a problem. That is, for example, if these are used as a casting material, the space will be smaller than the predetermined space of the mold, resulting in poor dimensional accuracy, or if they are used as a filling material, complete filling after curing may not be achieved.

On the other hand, compounds having a spiro-orthoester group and a compound having a spiro-orthocarbonate group have been proposed as resins that exhibit almost no volumetric shrinkage or, conversely, volumetric expansion upon curing (JP-A-58-49724). JP 58-109534, JP 58-33320, JP 59-49228, JP 59-184545).

However, these resins have a problem in that they have a high curing temperature and require a long time to cure. In order to solve this problem, the use of curing accelerators is being considered in order to lower the curing temperature and shorten the curing time. Attempts have been made to develop a curing accelerator for curing copolymerization of a compound and a curing agent, and several proposals have been made (Japanese Patent Application No. 60-34477,
However, no effective curing accelerator is known for compounds having a spiroorthocarbonate group.

[Problem that the invention seeks to solve]

The present invention relates to a resin composition containing a compound having a spiro-orthocarbonate group, which exhibits almost no volumetric shrinkage upon curing or expands in volume upon curing, and which can be cured at low temperatures and in a short period of time. The present invention aims to provide a curable resin composition.

(b) Structure of the invention [Means for solving the problems] - The present invention provides a compound having one or more spiroorthocarbonate groups in the molecule represented by the following formula [1] (hereinafter referred to as a spiroorthocarbonate compound). and at least one curing agent selected from the group consisting of organic polybasic acids and their anhydrides that function as curing agents for spiroorthocarbonate compounds, and curing accelerators in the following three groups (A) to (C). The resin composition is composed of one or more curing accelerators selected from the following.

(R1 and R2 in the above formula are the same or different divalent organic groups.) (A) Acetylacetone complex salt curing accelerator Acetylacetone complex salt, trifluoroacetylacetone complex salt, or hexafluoroacetyldiacetone complex salt. Old salt.

(B) Lewis acid curing accelerator BF4, PF6, As Fb- and SbF6-
An inorganic or organic salt having at least one selected from the following as an anion.

(C) Metal soap compound The thermosetting resin composition of the present invention has a feature that when the spiro-orthocarbonate group undergoes ring-opening polymerization and cures, the volume expands due to polymerization or the volume shrinkage is very small. In addition to this, it is possible to lower the curing temperature and shorten the curing time.

It is thought that the ring-opening polymerization reaction mainly proceeds as shown in the following reaction formula.

Next, the composition of the present invention will be explained in more detail.

First, the spiroorthocarbonate compound constituting the composition of the present invention will be explained.

R1 and R2 in the above formula [1] representing the spiroorthocarbonate compound used in the present invention are the same or different divalent organic groups, but preferably each R1
The carbon chain portion constituting the ring of formula [1] in R2 is preferably a divalent organic group having a skeleton having 2 to 4 carbon atoms. Further, various atoms or organic groups, including hydrogen atoms, alkyl groups, aryl groups, alkylene groups, and halogen atoms, may be bonded to the carbon atoms constituting these rings.

Of course, these groups themselves have ring structures,
It may contain atoms such as oxygen, nitrogen, sulfur, etc., or may be a residue of polyester, polyether, polyurethane, etc.

Specific examples of spiroorthocarbonate compounds that can be used in the present invention include the following compounds. 1.
4. 6. 9-tetraoxaspiro(4,4)nonane, 1,5,7.11-tetraoxaspiro(5,5)
Undecane, 1°6, 8. 13-tetraoxaspiro(6,6)tridecane, 1 4,6.10-tetraoxaspiro(4,5)decane, 2,7-simethyl-1
．． 4,6.9-Tetraoxaspiro (4,4E nonane,
2,3,7.8-Tetramethyl-1°4.6.9-tetraoxaspiroC4,4)nonane, 8-ethyl-8-hydroxymethyl-1°4.6.10-tetraoxaspiro(4) ,5) Decane, 3.9-diethyl-3,9-dihydroxymethyl-1,5,7,11-tetraoxaspiro(5,5)undecane, 3,3,9,9-tetramethyl-1,5 ,7,11-tetraoxaspiro(5,5)
Undecane, 8,8-dihydroxymethyl-1,4,6
, 10-tetraoxaspiro(4,5)decane, 3-methylene-1,5,7,11-tetraoxaspiro[5゜5]undecane 1,3-methylene-1,5,7゜12-
Tetraoxaspiro[5,6) dodecane, 3,9-
dimethylene-1,5,7,11-tetraoxaspiro
(5,5) Undecane, 8,1°0°19.20-tetraoxatetraspiro[5°2.2.5.2.23 Heneicosane, 1,4°6.10,12,15,16.
19-octaoxatrispiro (4,2,2,4,2,
2] Nonadecane, 3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-tetraoxaspiro (
5,5) Urethane of the following formula synthesized from undecane and hexamethylene diisocyanate.

* (Here, X' represents an integer of 1 or more).

[JP 58-10582, JP 59-49228,
See Foreign Polymer Research, 29.187 (1983)] These are examples of spiroorthocarbonate compounds, and are not intended to limit the scope thereof.

Next, the organic polybasic acids and organic polybasic acid anhydrides constituting the composition of the present invention will be described.

An organic polybasic acid blended as a curing agent in the composition of the present invention,
One type or two or more types of organic polybasic acid anhydrides can be selected and used. Furthermore, organic polybasic acids (such as trans-type acids) that do not form anhydrides can also be used.

The organic polybasic acid or its acid anhydride includes any one commonly used as a curing agent for epoxy compounds, such as the following.

Succinic anhydride, methylsuccinic anhydride, dodecenylsuccinic anhydride, dichlorosuccinic anhydride, azelaic anhydride, sebacic anhydride, itaconic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride , hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tricarballylic anhydride,
Trimellitic anhydride, pyromellitic anhydride, polybasic acids derived from these, or mixtures of two or more of these, as well as base acid anhydrides such as acetic anhydride and propiolene anhydride. of molecules obtained from the above acid anhydrides, such as mixtures with acids, benzoic anhydride, lyluic acid adducts of maleic anhydride, and compounds with structures in which these acid anhydrides are added to the hydroxyl groups of phenolic resins. Derivatives thereof having a carboxylic acid or its acid anhydride structure at the terminal or side chain can also be used.

Also tartaric acid, malic acid, tartronic acid, alkyl tartronic acid, α-methylmalic acid, β-methylmalic acid, α
-oxyglutaric acid, β-oxyglutaric acid, dicrotaric acid, α-oxysperic acid, α-oxysebacic acid,
Oxypolycarboxylic acids such as citric acid and isocitric acid can also be used.

The optimum proportion of the curing agent may be determined as appropriate depending on the chemical properties of the resin used and the properties required for the prepared curing composition and the cured product provided by it. Although the accelerating effect of the curing accelerator proposed in the invention is not particularly affected, the desirable blending ratio is the proportion of acid anhydride groups and carboxylic acid groups per total equivalent of spiroorthocarbonate groups in the composition. The total amount is 0.3 to 5 equivalents, more preferably 0.5 to 5 equivalents.
It is 3 equivalents.

Next, the curing accelerator constituting the composition of the present invention will be explained.

First, regarding (A) acetylacetone complex salt curing accelerator,
explain. Examples of the curing accelerator include acetylacetone complex salt, trifluoroacetylacetone complex salt, and hexafluoroacetylacetone complex salt. Among these, the acetylacetonate complex salts have the following structures: (I) monoacetylacetonate complex salt, (n) bisacetylacetonate complex salt, (■) trisacetylacetonate complex salt, (rV
) tetrakis acetylacetonate complex salts.

To specifically illustrate this acetylacetone complex salt, (I
) Monoacetylacetonate complex salts include tritium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, dimethyl acetylacetonate, and dimethyl gallium acetylacetonate. (II
) Bisacetylacetonato complex salts include copper bisacetylacetonate, beryllium bisacetylacetonate, magnesium bisacetylacetonate, zinc bisacetylacetonate, dioxymolybdenum bisacetylacetonate, di-nokel bisacetylacetonate, and bisacetyl. These include calcium acetonate, barium bisacetylacetonate, dichlorotin bisacetylacetonate, and oxyhanadium bisacetylacetonate. (■) Trisacetylacetonato complex salts include trisacetylacetonatotitanium, trisacetylacetonatocerium,
These include trisacetylacetonatomanganese, trisacetylacetonatoiron, trisacetylacetonatocohardt, and trisacetylacetonatoaluminum. Also(
IV) Tetrakis acetylacetonate t=salt:
Examples include tetrakisacetylacetonatosilconium and tetrakisacetylacetonatotrium.

On the other hand, examples of the trifluoroacetylacetone complex salt and the hexafluoroacetylacetone complex salt include metal complex salts in which the ligand is represented by the following structural formula.

Trifluoroacetyl hexafluoroacetylacetonato complex salt Acetonate complex salt (n is an integer of 1 to 4, and M' represents an n-valent metal or a metal complex salt.) Examples of these include trifluoroacetylacetonato complex salt. Examples of complex salts include bis-trifluoroacetylacetonatocopper, bis-trifluoroacetylacetonatomagnesium, bis-trifluoroacetylacetonatomanganese, and tris-trifluoroacetylacetonatoiron. Examples include copper fluoroacetylacetonate, manganese bis-hexafluoroacetylacetonate, nickel bis-hexafluoroacetylacetonate, and iron iron tris-hexafluoroacetylacetonate.

Next, (B) BF4- as a Lewis acid curing accelerator.
, PFb, As Fb, 5l) Fb- as an anion, for example, metal salts such as lithium, zinc, nickel, sodium, potassium, tin, lead, copper, iron, etc. , or quaternary ammonium salts such as ammonium, tetraethylammonium, tetraethylammonium, tetra-n-propylammonium, and tetra-n-butylammonium, aryldiazonium salts such as benzenediazonium and p-chlorobenzenediazonium, and diphenyliodonium, Examples include diarylhalonium salts such as ditolyliodonium.

Next, the metal soap curing accelerator (C) will be explained.

Metal soap curing accelerators include divalent or higher valent metals, such as alkaline earth metals or heavy metals such as aluminum, calcium, manganese, lead, zinc, and tin, octylic acid (2-ethylhexylic acid), stearic acid, Examples include organic acid salts bound with organic acids such as naphthenic acid, tall oil fatty acid, and soybean oil fatty acid. Many of these metal soap compounds are commercially available, but in general, oxides, chlorides, hydroxides, metal powders, or sulfates of each metal are mixed with organic acids by melting, double decomposition, or direct methods using catalysts. It is produced by reacting with Examples of these include aluminum octylate, calcium octylate, cobalt octylate, iron octylate, magnesium octylate, manganese octylate, lead octylate, zinc octylate, zirconium octylate, tin octylate, nickel octylate, and stearic acid. Aluminum, calcium stearate, cobalt stearate, iron stearate, magnesium stearate, manganese stearate, lead stearate, zinc stearate, tin stearate, nickel stearate, barium stearate, copper stearate,
Calcium naphthenate, cobalt naphthenate, iron naphthenate, magnesium naphthenate, manganese naphthenate,
Lead naphthenate, zinc naphthenate, nickel naphthenate,
Examples include copper naphthenate, calcium oleate, and zinc oleate.

The amount of the curing accelerator blended in the composition of the present invention is not particularly limited, but it is usually composed of a spiro-orthocarbonate compound, an organic polybasic acid, and an anhydride-based curing agent thereof. It is preferably in the range of 0.1 to 10 parts, more preferably 0.5 to 5 parts, based on 100 parts by weight (the same applies hereinafter) of the resin content.

There are no particular restrictions on the method of blending the curing accelerator, and the objective can be achieved by uniformly dispersing or dissolving the curing accelerator. For example, by heating the spiro-orthocarbonate compound, the above-mentioned curing agent, or a mixture thereof at a temperature higher than the melting point (softening point), and uniformly dispersing or dissolving a predetermined amount of the curing accelerator, the objective can be achieved. A composition is obtained. Moreover, it is also possible to uniformly disperse it by a normal mechanical kneading method at room temperature. They may be combined and mixed uniformly,
The curability of the resulting curable composition is not particularly affected.

The curing accelerator can be used in the formulation as a single solid powder, or if necessary, it can be uniformly dissolved or dispersed in a solvent and mixed into the resin component.

In this case, solvents that can be used include general organic solvents such as acetone, methyl ethyl ketone, benzene, toluene, xylene, propylene carbonate, and ethylene glycol, as well as polymeric compounds that are liquid at room temperature such as polyethylene glycol and polypropylene glycol. be.

Further, the composition of the present invention may contain other components.

For example, the composition of the present invention may further contain a cationically polymerizable compound other than the spiroorthocarbonate compound, and there are no particular restrictions on the type thereof. Examples of compounds suitable for blending include epoxy compounds such as phenylglycidyl ether, bisphenol A epoxy resin, Talezol novolac epoxy resin, alicyclic epoxy resin, and polyglycidyl ether of polyhydric alcohol;
Spiroorthoester compounds known from JP-A-57-67628, etc., bicycloortho-ester compounds known from JP-A-58-134113, etc., lactones such as ε-caprolactone, cyclic ethers such as oxetane, tetrahydrofuran, etc. etc. The blending ratio of these cationically polymerizable compounds to the spiro-orthocarbonate compound may be selected at any ratio in order to match the volume change and other physical properties to the intended use.

Other additives for the composition of the present invention include fillers such as quartz powder, alumina, and β-eucryptite, as well as dyes and flame retardants.

Although there are no particular limitations regarding the curing temperature of the resin composition of the present invention, curing is usually performed at room temperature to 250°C.

[Embodiments of the invention]

Examples of the present invention will be described below along with comparative examples.

Example 1 and Comparative Example 1 (Example 1) 3,3,9.9-tetramethyl-1,5 represented by the following formula
, 52 parts of 7,11-tetraoxaspiro[5,5]undecane and "RecaresinTM" which is an organic polybasic acid anhydride.
EGJ [part name manufactured by Shinjo Rika Co., Ltd.] was prepared. The amount of organic polybasic acid anhydride group charged per equivalent of spiroorthocarbonate group in this composition is 1 equivalent. This composition was reacted in an oil bath at 150°C to obtain a polymer. Table 1 shows the results of measuring the gelation time of this polymer.

Note that the gelation time is the time it takes for the composition to lose its fluidity after the composition is placed in a test tube and subjected to a heating reaction as described above.

The volume change during curing of the composition of this example was an expansion of 1 to 2%.

(Comparative Example 1) When a similar test was conducted on a composition using the spiro-orthocarbonate compound and curing agent shown in Example 1 but without the addition of a curing accelerator, the gelation time was as follows.
It took about 60 minutes.

Example 2 and Comparative Example 2 (Example 2) 8,10.19.20-tetraoxatrispiro[5,2,2,'5.2.2)heneicosan-2.14-diene 63 shown by the following formula 37 parts of methylhexahydrophthalic anhydride and 1 part of each of the accelerators shown in Table 2 were added to prepare a curing composition. The amount of acid anhydride group charged per equivalent of spiroorthocarbonate group in this composition is 1 equivalent. This composition was heated and melted at 120°C to prepare a curing composition.

These were reacted for 1 hour in an oil bath at 150°C to obtain a viscous polymer. Table 2 shows the results of determining the average molecular weight of the products by HLC (high performance liquid chromatography) analysis of these polymers. The average molecular weight of the produced polymer was calculated as a polystyrene equivalent weight average molecular weight from HLC analysis under the following measurement conditions.

Equipment 7 Yoso Soda Kogyo Co., Ltd. HLc-802UR column, TSKF gel G-3000H+ G-2000H
Eluent: Tetrahydrofuran Flow rate: 1ml! /min The volume change during curing of the composition of this example is 0.5 to 1%.
It was expansion.

(Comparative Example 2) Further, as a comparative example, a similar test was conducted on a composition in which no curing accelerator was added, and the average molecular weight was 320.

Table 2 Example 3, Comparative Example 3 (Example 3) Same as Example 1 3,3,9.9-tetramethyl-1,5
,7,11-tetraoxaspiro[5.

5] BEF, which is a polyhydric carboxylic acid, is added to 54 parts of underiched
-P-210C manufactured by Toagosei Chemical Industry Co., Ltd., product name]
46 parts of bisacetylacetonatodioxymolybdenum, tetra-n-butylammonium tetrafluoroborate, or zirconium octylate were added in an amount of 0.0 parts each. 5 parts were added and mixed uniformly in a mortar to obtain a curing composition.

The amount of polyhydric carboxylic acid group charged per equivalent of spiroorthocarbonate group in this composition is 0.7 equivalent. This composition was reacted at 130°C to obtain a polymer. When the absorption change of this polymer was followed by IR analysis, a peak at 1260 cm-', which corresponds to the absorption of the carbonate group generated by ring-opening of the spiro-orthocarbonate group, was observed at 5 minutes, 7 minutes, and 5 minutes, respectively. generated. This can be seen from the fact that ring-opening polymerization occurred due to these. The volume change of the composition of this example during hard death is 1 to 2% expansion.

(Comparative Example 3) Further, as a comparative example, a similar experiment was conducted in the case where no curing accelerator was added, and the above peak did not appear even after 60 minutes had passed.

Examples, Comparative Example 4 (Example 4) Spiroorthocarbonate compound 45 used in Example 2
1 part, 40 parts of acid anhydride "Recaresin MTA-18" (manufactured by Shin Nippon Chemical Co., Ltd., trade name), Talesol novolac type epoxy resin YDCN-701 [manufactured by Tobu Kasei Co., Ltd.]
Co., Ltd., trade name] 1 part of each of the curing accelerators shown in Table 3 were added to 15 parts of the curing composition to prepare a curing composition. The amount of acid anhydride group charged per equivalent of spiro-orthocarbobutyl group in this composition is 1 equivalent. This composition was reacted for 2 hours in an oil bath at 120°C to obtain a cured product. An acetone immersion test was conducted on these cured products.

In the acetone immersion test, the sample is soaked in acetone at room temperature for 2 hours.
This was done by measuring the dissolved content after 4 hours of immersion.

Weight of dissolved content Dissolution rate (%) = 'X100 Weight of original sample The results are shown in Table 3. The volume change during curing of the composition of this example was an expansion of 0.5 to 1%.

(Comparative Example 4) Furthermore, as a comparative example, a similar test was conducted in the case of no additives. As shown in Table 3, the dissolution rate was 100%.
This shows that no polymerization has occurred.

Table 3 (c) Effects of the invention The resin composition according to the invention can obtain the desired cured product under milder conditions, that is, at lower temperatures, and in a shorter time than with conventionally used resin compositions. can. In addition, there is almost no volumetric shrinkage during curing, for example, dimensional accuracy during molding is good, internal stress and gaps are low during cast molding, good adhesion when used as a paint, and good adhesiveness when used as an adhesive. It is possible to form a cured product with advantages such as good properties, and is useful in various fields.

Claims (1)

[Scope of Claims] At least one compound having one or more spiroorthocarbonate groups in the molecule represented by the following formula [1], and a curing agent selected from the group consisting of organic polybasic acids and their anhydrides. A thermosetting resin composition comprising at least one type and a curing accelerator consisting of one or more compounds arbitrarily selected from the following three groups A, B, and C. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1 and R^2 in the above formula are the same or different divalent organic groups.) (A) Acetylacetone complex salt compound Acetylacetone complex salt, trivalent Fluoroacetylacetone complex salt or hexafluoroacetylacetone complex salt. (B) Lewis acid compounds BF_4^-, PF_6^-, AsF_6^- and Sb
An inorganic or organic salt having at least one selected from F_6^- as an anion. (C) Metal soap compound