JPH02187454A - Resin composition and cured product thereof - Google Patents

Abstract

PURPOSE:To obtain a resin composition capable of suppressing molded product shrinkage without whitening, thus suitable for precision parts. IC sealers, etc., by incorporating a unsaturated polyester or vinyl ester resin with a specific spiro compound. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt., on a solid basis, of a unsaturated polyester or vinyl ester resin 100-600 in unsaturated group equivalent with (B) 10-200 (pref. 30-150) pts.wt. of a spiro compound of the formula (R is H, lower alkyl or phenyl).

Description

Detailed Description of the Invention (Field of Industrial Application) The BA of the present invention relates to a resin composition consisting of a specific spiro compound (4) and an unsaturated polyester or vinyl ester resin (CB), and more specifically relates to an unsaturated polyester or vinyl ester resin (CB). The present invention relates to a resin composition that has excellent precision moldability and has improved shrinkage of cured polymer products, which is a drawback of polyester or vinyl ester resins.

(Prior Art and its Problems) Thermosetting resins such as unsaturated polyester resins and vinyl ester resins have the disadvantage that during polymerization, the volume of the molded product shrinks by 6 to 7 inches. Therefore, if the volume shrinkage is large during polymerization, the molded product may have problems such as a lack of dimensional accuracy or cracks in the case of a large cast product.

In recent years, in the field of precision molding such as electronic materials (encapsulants), there has been a demand for materials that have no distortion at all.

However, unsaturated polyester resins and vinyl ester resins, which are in-shell thermosetting resins, cannot be used in these fields because they shrink significantly.

Therefore, by improving this point, it will be possible to apply unsaturated polyester resins and vinyl ester resins to precision molded products and large-sized molded products, so we have been researching ways to reduce the shrinkage of unsaturated polyester resins and vinyl ester resins. is being done. For example, the method involves blending thermoplastic polymers, causing the thermoplastic polymer to foam with the heat generated when the resin hardens, and then canceling out the polymerization and shrinkage of the thermosetting resin.
This reduces the shrinkage rate. However, a drawback of this method is that the molded product becomes white due to foaming of the thermoplastic resin. It is impossible with this method to control the shrinkage rate without causing whitening.

(!IJI! Means for Solving the Problem) Therefore, the present inventors have discovered that when molded products are made from unsaturated polyester or vinyl ester resins, it is possible to suppress shrinkage of the molded products without whitening the surface. As a result of intensive research into resin compositions, the present invention has been completed.

That is, the present invention provides a resin composition comprising: (4) a spiro compound represented by the general formula CI) (wherein R represents hydrogen, a lower alkyl group, or a phenyl group); and ω) an unsaturated polyester or vinyl ester resin. It is something that provides something.

(Structure) As mentioned above, the spiro compound (4) represented by formula (1) of the present invention is a compound in which R is hydrogen, a C4-5 lower alkyl group such as methyl, ethyl, butyl, or a phenyl group. a,! l) and (B) may be used alone or in combination. The amount is the solid content of component (B) 10
Preferably 10 to 200, particularly 30 to 1, per 0 parts by weight
50 parts by weight are used. If the amount is less than 10 parts by weight, the resulting molded product will not have the effect of low shrinkage, and if it is more than 200 parts by weight, there will be no change in the low shrinkage, which is uneconomical.

The unsaturated polyester of the component (B) of the present invention is α.

It is an unsaturated I-lyester resin that does not contain or contains a β-unsaturated monomer.

The unsaturated polyester resin (B) used in the present invention includes α,β-unsaturated dibasic acid or its acid anhydride;
Unsaturated diester 30 produced by polycondensation of an aromatic saturated dibasic acid or its acid anhydride and glycols, and in some cases using an aliphatic or alicyclic saturated dibasic acid as the acid component. ~80 parts by weight, α, β
- Examples include those obtained by dissolving in 70 to 10, preferably 20 to 60 parts by weight of an unsaturated monomer.

As the α,β-unsaturated dibasic acid or its acid anhydride,
maleic acid, maleic anhydride, fumaric acid, itaconic acid,
These include citraconic acid, chlormaleic acid, and their esters, and examples of aromatic saturated dibasic acids or their acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endo Examples of aliphatic or alicyclic saturated dibasic acids include methylenetetrahyde, phthalic anhydride, rhodanated phthalic anhydride, and esters thereof; aliphatic or alicyclic saturated dibasic acids;
Examples include malonic acid, conolic acid, adipic acid, sepacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, each of which may be used alone or in combination. Glycols and L-"C are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-
1,3-diol, neointyl glycol, triethylene glycol, tetraethylene glycol, 1,5-
Bentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A1 ethylene glycol carbonate, 2,2-di+4-hydroxypropoxydiphenyl÷propane, etc., which are used alone or in combination, but in addition Oxides such as ethylene oxide and propylene oxide can also be used. Polycondensates such as I-diethylene terephthalate can also be used as part of the glycols and acid components. Examples of α,β-unsaturated monomers include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, and acrylonitrile. , vinyl monomers or vinyl oligomers capable of crosslinking with unsaturated polyesters such as vinyl compounds such as methacrylonitrile, and allyl compounds such as diallyl phthalate, diallyl 7-malate, diallyl succinate, triallyl cyanurate, etc. are used in combination, preferably styrene is used.

The unsaturated polyester or vinyl ester resin (B) is
Preferably, it has an unsaturated group equivalent of 100 to 600.

If the unsaturated group equivalent is less than 100, it cannot be synthesized, and if it is more than 600, a material with sufficient strength as a molding material cannot be obtained.

The vinyl ester resin 0) of the present invention may or may not contain α, β-, and β-monomers, and is manufactured by a known method. , epoxy resin and acrylic acid or methacrylic acid as components, or unsaturated or saturated polyester as components of saturated dicarboxylic acid and unsaturated dicarboxylic acid, or either dicarboxylic acid and polyhydric alcohol. and an epoxy compound containing α, β-, β-carpic acid ester groups.
It is acrylate. Examples of the saturated dicarboxylic acid having no active unsaturated group include orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and cecinic acid. Examples of unsaturated dicarboxylic acids having an active unsaturated group include fumaric acid,
Examples include maleic acid and itaconic acid. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, 1,5-pentadiol, 1,3-butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-7'rono Examples include diol, diethylene glycol, triethylene glycol, a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A, and glycerin.

Typical examples of the epoxy resin include bisphenol A diglycidyl ether, its high molecular weight homologues, and noblack type polyglycidyl ethers.

Glycidyl methacrylate is a typical example of the epoxy compound having an α,β-unsaturated carenoic acid ester group.

The resin of component (B) of the present invention may include the above α,
β-unsaturated monotopes, thickeners, colorants, reinforcing agents, fillers,
A curing catalyst, a curing accelerator, a curing retardant, an internal mold release agent, a shrinkage reducing agent, etc. may be added.

As a thickener, it increases the molecular weight by chemically bonding with the hydroxyl group, carboxyl group, ester bond, etc. possessed by unsaturated polyester or vinyl ester resin to form linear or partially cross-linked bonds. For example, diisocyanates such as toluene diisocyanate, metal alkoxides such as aluminum isozoloxide, titanium tetrabutoxy, divalent metal oxides such as magnesium oxide, calcium oxide, and beryllium oxide, Examples include divalent metal hydroxides such as calcium hydroxide. The amount of the thickener used is usually 0.2 to 10 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the unsaturated polyester or vinyl ester resin (6). And if necessary, a small amount of a highly polar substance such as water can be used as a thickening agent.

As the colorant, conventionally known organic and inorganic dyes and pigments can be used, but among them, unsaturated polyester and vinyl ester resins (
Those that do not significantly hinder the curing of B) are preferred.

The reinforcing material used in the present invention generally includes glass fiber, but also vinylon, polyester,
Organic fibers such as phenol, asbestos, car? Examples include fibers.

Fillers include calcium carbonate powder, clay alumina powder, crushed stone powder, talc, sulfuric acid, and silica powder.
For glass powder, glass peas, mica, and hardening accelerators, metal compounds are added as necessary. Examples of such metal compounds include cobalt naphtonate, cobalt octonate, divalent acetylacetone cobalt,
Unsaturated polyester resins such as trivalent acetylacetone cobalt, potassium hekynate, zirconium naphtonate, zorconium acetylacetonate, vanadium naphtonate, vanadium octonate, panazoum acetylacetonate, vanadyl acetylacetonate, lithium acetylacetonate, etc. Metal compound accelerators commonly used in
It may be combined with known accelerators such as β-diketones.

The amount of the curing accelerator added is appropriately adjusted depending on the curing time, but it is preferably 0.0001-0 as the metal component.
．． It is 12 parts by weight. This curing accelerator may be omitted or may be used when molding is performed at medium temperature or higher (40° C. or higher). Known materials include aluminum hydroxide, cellulose thread, crushed sand, river sand, kansui stone, astronomical stone waste, and crushed stone.
Among these, glass powder, aluminum hydroxide, barium sulfate, etc. are preferred because they provide transparency during facilitation.

The curing catalyst is one that acts on the unsaturated polyester or vinyl ester resin (B), such as an azo compound such as azoisobutyronitrile, tert-butyl 1
4-benzoate, tertiary octoate,
Benzoyl peroxide, methyl ethyl ketone 9-
Examples include organic peroxides such as oxide, dicumyl/4'-oxide, etc., and 0.1 parts by weight per 100 parts by weight of unsaturated polyester or vinyl ester resin (6).
It can be used in a range of 4 parts by weight, preferably 0.3 to 3 parts by weight.

Examples of the curing retarder include hydroquinone, toluhydroquinone, tert-butylcatechol, copper naphthenate, etc., and it is preferably used in an amount of 0.0001 to 0.1 part by weight per 100 parts of ω) component resin. be done.

Examples of the internal mold release agent include conventionally known ones such as higher fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters.
It can be used usually in an amount of 0.5 to 5 parts by weight per 100 parts by weight of unsaturated polyester or vinyl ester.

The shrinkage reducing agent is a thermoplastic resin, and specific examples include lower alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate, styrene, vinyl chloride, and acetic acid. Homopolymers or copolymers of monomers such as vinyl, at least one of the vinyl monomers and lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, acrylonitrile, methacrylaterile, At least IF of monomers such as acrylic acid, methacrylic acid, and cetylstearyl methacrylate! Examples include copolymers of , cellulose acetate butyrate, cellulose acetate tetrabionate, polyethylene, polypropylene, and saturated polyester. These may be added as necessary, depending on the intended use, so long as they do not impair the effects of the present invention.

K for producing a molded article from the resin composition of the present invention is an unsaturated diliester or vinyl ester resin (B) with the formula [1]
A sulfur compound shown by is added, a curing retarder is added as necessary to prepare a resin composition, and a curing catalyst is further added. A molded article can be obtained by casting the obtained resin composition into a mold and heat-curing it, preferably at 60 to 150° C. for 5 to 30 minutes.

(Effects) The resin composition of the present invention can provide non-shrinkable molded articles made of unsaturated polyester or vinyl ester without foaming or whitening, unlike conventional low-shrinkage agents for thermoplastic resins.

Therefore, it can be widely used in molding fields that require precision moldability, such as precision parts, IC sealants, lenses, dental materials, and general laminate products, cast products, composite materials, etc. (Example) The present invention will be explained in detail below with reference to Examples.
"Parts" and "Chi" are based on weight.

Example 1 Propylene glycol and maleic anhydride were reacted in a molar ratio of 1.1:1.0 according to a conventional method to obtain an unsaturated polyester (1) having an acid value of 27.

The unsaturated polyester resin (1) had an unsaturated group equivalent of about 156.

30 parts of unsaturated polyester (1), 20 parts of styrene monomer, 2-methylene-7-methyl-1,4,6°9
50 parts of -tetraoxaspiro(4,4]nonane and 0.01 part of nohydroquinone were added to obtain composition A.

To 100 parts of Composition A, 2.0 parts by weight of ditertiary butyl arm oxide (trade name, Perbutyl 6, manufactured by NOF Corporation) was added as an organic peroxide, and the mixture was cast into a mold. It was heated and cured at 120°C for 10 minutes.

The specific gravity was separately measured and the volumetric shrinkage rate during curing was determined according to the following formula, and the results are shown in Table 1.

Volume shrinkage rate = (1 - (specific gravity of resin composition / specific gravity of cured product)) .0:1.0
When the acid value reaches 2, 2,2-
An unsaturated polyester (IQ) having an acid value of 6 was obtained by mixing dimethyl-1,3-propanediol, propylene glycol, and fumaric acid in a molar ratio of 1.0:1.4:3.0. The unsaturated group equivalent weight of II) was approximately 239.

Next, 80 parts of unsaturated polyester (II), 20 parts of 2-methylene-7-methyl-1,4,6,9-tetraoxaspiro(4,4)nonane, and 0.01 part of nohydroquinone were added. , Composition B was obtained.

Composition B: 2.0 parts of ditertiary-butyl peroxide was added to 100 parts, poured into a mold, and cured by heating at 120° C. for 10 minutes.

The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.
It was shown to.

Example-3 2,2-dimethyl-1,3-propanediol and isophthalic acid were mixed in a molar ratio f 1.6:0 according to a conventional method.
．． When the acid value reaches 2 after reacting at a ratio of 8 to 2,
2-dimethyl-1,3-propanediol, propylene glycol, fumaric acid molar ratio 0.7:1.0:2.
An unsaturated polyester (2) having an acid value of 6 was obtained at a ratio of 2 to 2. The unsaturated group equivalent of this unsaturated polyester (2) was about 295.

Unsaturated polyester ([) 50 parts, 2-methylene-7-
Methyl-1,4,6,9-tetraoxaspiro [4゜4
] Composition C was obtained from 50 parts of nonane and 0.01 part of hydroquinone.

2.0 parts of ditertiary-butyl peroxide as an organic peroxide was added to 100 parts of the composition C, and the mixture was poured into a mold and cured by heating at 120°C for 10 minutes.

The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-IK.
Indicated.

Example-4 Diclite UE-35 as vinyl ester resin
05 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) 70 parts and 30 parts of 2-methylene-7-methyl-1,4,6,9-tetraoxaspiro[4,/D nonane to obtain a cylindrical acid compound. Ta.

To 100 parts of Composition D, 2.0 parts of ditertiary butyl or monooxide was added as an organic peroxide, and the mixture was poured into a mold and cured by heating at 120° C. for 10 minutes.

The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.
It was shown to.

Comparative Example-1 30 parts of the unsaturated polyester (1) obtained in Example-1, 70 parts of styrene monomer, and 0.01 part of dihydroquinone
1, and 2.0 parts of ditertiary butylene and monooxide were added, and the mixture was poured into a mold and cured by heating at 120° C. for 10 minutes. The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.

Comparative Example-2 Nine unsaturated z+7 ester (IN) obtained in Example-2
To 100 parts, 0,901 parts of high-r quinone was added, and the mixture was cast into a mold and cured under the same conditions as in Example 2. The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.

Comparative Example-3 2.0 parts of ditertiary-butyl peroxide was added to 100 parts of a composition consisting of 50 parts of the unsaturated polyester obtained in Example-3, 50 parts of styrene monomer, and 0.01 part of hydroquinone. Example-
It was cured under the same conditions as No. 3. The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.

Comparative Example-4 Vinyl ester resin of Example-4 (Dicklite Uz
2.0 parts of ditertiary chil nona-oxide was added to 3sos), which was then cast into a mold and cured under the same conditions as in Example 4. The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.

Comparative Example-5 70 parts of the vinyl ester resin used in Example-4, 30 parts of a low shrinkage agent (polystyrene solution, Mn=57000, styrene solution, nonvolatile content 50%), and 2.0 parts of ditertiary-butyl peroxide. The mixture was added, cast into a mold, and cured under the same conditions as in Example-4. The volumetric shrinkage rate was measured in the same manner as in Example-1, and the results are shown in Table-1.

Table-!

Claims (1)

[Claims] 1. (A) General formula [I] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (R represents hydrogen, a lower alkyl group, or a phenyl group) The spiro compound shown by (2) Unsaturated polyester or vinyl ester resin A resin composition consisting of. 2. A cured product comprising the resin composition according to claim 1.