JPS617352A - Unsaturated polyester composition - Google Patents

Abstract

PURPOSE:To obtain a composition low in volume shrinkage in curing, free from crack development, highly adhesive to glass plate, suitable for application to safety glass, by using an unsaturated polyester modified with 3,6-endomethylene- 1,2,3,6-tetrahydrophthalic acid (anhydride). CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of a modified unsaturated polyester prepared by the reaction of an unsaturated acid with a product derived from dehydrating condensation between 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid (anhydride) and an alcohol component, with (B) pref. 0.1-2pts.wt. of an organic peroxide (e.g. methyl-ethyl ketone peroxide) and/or (C) pref. 0.01-3pts.wt. of a photopolymerization initiator (e.g. diphenyl disulfide) and, if necessary, (D) curing promotor (e.g., cobalt naphthenate), crosslinkable monomer (e.g. styrene), and/or polymerization inhibitor (e.g., hydroquinone).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to unsaturated polyester compositions, and more particularly to unsaturated polyester compositions containing 3,6-nindomethylene-1,2°3,6-tetrahydrophthalic anhydride or 3,6-endomethylene Methylene-
The present invention relates to an unsaturated polyester composition containing an unsaturated polyester modified with 1,2,3,6-titrahydrofucric acid, the cured product of which has excellent adhesiveness to a glass plate.

(Background of the Invention) Unsaturated polyester resins, that is, mixtures of unsaturated polyesters and crosslinkable monomers, are cured at room temperature or by heating using polymerization initiators such as organic peroxides, and are used in a wide variety of applications. It is being

However, unsaturated polyester resins have a
Since the volume shrinks by ~10%, molded products and cast products obtained using these products are likely to warp or crack, and they also have poor adhesion to glass plates, so they are not suitable for laminated glass or television screens. It is considered unsuitable for castings with safety glass plates.

Conventionally, compositions consisting of unsaturated polyester and dimethacrylate of mono- or diethylene glycol have been known for improving adhesion to glass plates, for example for coating window glass or television screens (Belgium Patent No. 651,875). issue). Furthermore, a composition consisting of unsaturated polyester and glycidyl methacrylate is also known as a resin for explosion-proofing treatment of cathode ray tubes (Patent No. 81
No. 9166).

However, these resin compositions have the disadvantage that their adhesive strength with glass plates is insufficient and they tend to peel off from the glass.

(Object of the Invention) The object of the present invention is to eliminate the drawbacks of the above-mentioned prior art, and to provide an unsaturated polyester composition that has a low volumetric shrinkage rate, does not cause cranking, and has excellent adhesiveness to glass plates. It is about providing.

(Summary of the Invention) In order to achieve the above object, the present inventors have conducted various research and found that
The present invention was achieved by discovering that unsaturated polyester modified with 3,6-nindomethylene-1,2,3°6-tetrahydrophthalic anhydride has relatively good adhesion to glass plates.

The present invention provides 3,6-nindomethylene-1.2゜3.6-
Tetrahydrophthalic anhydride or 3,6-nindomethylene-1. 2. 3. Unsaturated polyester modified with 6-tetrahydrophthalic acid and organic peroxide and/or
Or it relates to an unsaturated polyester composition containing a photopolymerization initiator.

The composition of the present invention may contain a crosslinkable monomer.

3,6-nindomethylene-1.2, used in the present invention
The unsaturated polyester modified with 3.6-tetrahydrophthalic anhydride or 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid is usually 3.6-nidomethylene-1. 2. 3゜6-tetrahydrophthalic anhydride or 3.6-nindomethylene-1.2. '3.6
- Obtained by reacting an unsaturated acid with a reaction product obtained by subjecting tetrahydrophthalic acid and an alcohol component to a dehydration condensation reaction. Other unsaturated acids and/or saturated acids may be used as necessary during the dehydration condensation reaction.

Examples of alcohol components include ethylene glycol,
Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1.5
-bentanediol, 1,6-hexanediol, 2,
2.4-) Dimethyl-1,3-bentanediol, trimethylolpropane, glycerin, water-added bisphenol A, etc. are used. As the unsaturated acid, for example, acrylic acid, methacrylic acid, etc. are used.

3.6-Nindomethylene-1. 2. 3. 6-tetrahydrophthalic anhydride or 3,6-endomethylene-
Although there is no particular restriction on the reaction amount ratio of 1,2,3,6-tetrahydrophthalic acid and alcohol component, the latter is preferably 1 to 2.5 moles per 1 mole of the former.

Other unsaturated acids that may be used as necessary include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. Examples of saturated acids include phthalic acid,
Phthalic anhydride, adipic acid, cepatic acid, etc. are used.

The above-mentioned modified unsaturated polyester is 3,6-nindomethylene-1. 2. 3. 6-tetrahydrophthalic anhydride or 3,6-nindomethylene-1.2,3.6
It can also be obtained by reacting -tetrahydrophthalic acid with a monoepoxy compound having an unsaturated bond, such as glycidyl methacrylate.

Note that 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride is produced by thermally decomposing dicyclopentadiene at 170°C to 180°C to form cyclopentadiene, which is then heated at 20°C to 180°C. It is obtained by a )iels-Alder reaction with maleic anhydride at 40° C. for 2 hours. The product is Himic Anhydride manufactured by Hitachi Chemical.

In this reaction, if maleic acid is used instead of maleic anhydride, 3.6-nindomethylene-1.2,3.6
-tetrahydrophthalic acid is obtained. These compounds are known.

Examples of the organic peroxide used in the present invention include methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide, acetylacetone peroxide, t
-butyl peroxybenzoate, benzoyl peroxide and the like. These compounds may be used alone or in combination of two or more. The amount of organic peroxide added is not particularly limited, but is preferably 0.1 to 2 parts by weight per 100 parts by weight of unsaturated polyester.

Examples of the photopolymerization initiator used in the present invention include diphenyl disulfide, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-
Propyl ether, benzoin isopropyl ether,
Benzoin 5ec-butyl ether, benzoin-2-
Examples include pentyl ether, benzoin cyclohexyl ether, dimethylbenzyl ketal, and the like. These compounds may be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is not particularly limited, but is preferably 0.01 to 3 parts by weight per 100 parts by weight of the unsaturated polyester. The organic peroxide and the photopolymerization initiator may be used together if necessary.

A curing accelerator may be added to the composition of the present invention, if necessary. The curing accelerator used in this case may be any substance that decomposes the organic peroxide by redox reaction and facilitates the generation of active radicals, such as cobalt naphthenate, vanadium naphthenate, dimethylaniline, Diethylaniline, toluidine, etc. are used.

Furthermore, the composition of the present invention may further contain a crosslinkable monomer. Examples of crosslinkable monomers include ebastyrene, vinyltoluene, divinylbenzene, chlorostyrene, t-butylstyrene, methyl methacrylate, ethyl methacrylate, ethylene glycol diacrylate, ethylene glycol methacrylate, 1. 6-hexanethiol dimethacrylate, trimethylolparopane triacrylate, etc. are used.The amount of the crosslinking monomer added is not particularly limited, but is 0 to 15 parts by weight per 100 parts by weight of unsaturated polyester. is preferred.

The composition of the present invention may optionally contain, for example, hydroquinone,
p-benzoquinone, t-butylcatechol, di-t-butylcatechol, hydroquinone 7-methyl ether,
May contain polymerization inhibitors such as hydroquinone monoethyl ether and mono-t-butylhydroquinone.
The amount of the polymerization inhibitor added is not particularly limited, but is preferably 0 to 0.01 parts by weight per 100 parts by weight of the unsaturated polyester.

(Effect of the invention) The composition of the present invention has 3,6-nindomethylene-1.2,
By containing an unsaturated polyester modified with 3.6-tetrahydrophthalic anhydride or 3.6-endomethylene-1,2,3,6-tetrahydrophthalic acid, it is possible to crosslink with the unsaturated polyester during curing. Compared to conventional unsaturated polyester resins obtained from polyester monomers, the volumetric shrinkage rate can be significantly lowered from, for example, 5 to 10% to 3% or less. It has the advantage of excellent adhesion to the board. Therefore, the composition of the present invention can be suitably used for casting laminated glass, TVIL screens, and safety glass plates.

(Example of the invention) Parts in the examples mean parts by weight.

Example 1 3.6-Nindomethylene-1. 2. 3. 1 mole of 6-tetrahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd., trade name Heiminkic anhydride) and 2.1 moles of diethylene glycol were reacted with stirring at 200°C in a nitrogen gas stream to form a reactant with an acid value of 11.3. Obtained. This was reacted with 2 moles of acrylic acid in a nitrogen gas stream at 150°C with stirring to obtain an unsaturated polyester (A) with an acid value of 7.8.

This unsaturated polyester (A>100 parts) was added with dimethylbenzyl ketal (manufactured by Nagashio Sangyo, IRGACURE 6).
51) 0.2 part was added to obtain a composition (A-1) of the present invention.

On a transparent window glass plate with a thickness of 3 tm
Hollow out the size of the crane and place the resulting spacer.

Inject the composition (A-1) into this hollowed out part, cover it with a transparent window glass plate with a thickness of 3 m x 50 mm x 50 fi, and fasten the glass plates with a stopper.
W/■ ultraviolet lamp (manufactured by Toshiba Denzai Co., Ltd., HlooOL>
25σ and irradiated for 180 seconds.

The obtained unsaturated polyester injection plate is colorless and transparent, has no cracks (no peeling from the glass plate, and has a temperature of 48°C at 150°C).
No peeling occurred from the glass plate even after continuous standing for hours. The volume shrinkage rate was 2.2%.

Example 2 To 100 parts of the unsaturated polyester (A) obtained in Example 1, methyl ethyl ketone peroxide (NOF type,
55% by weight of methyl ethyl ketone peroxide and 45
A composition (A-2) of the present invention was obtained by adding 0.3 part of a mixture with dimethyl phthalate (% by weight).

Thereafter, the composition (A-2), which was treated in the same manner as in Example 1 and injected between the glass plates, was left in an electric dryer at 80°C for 300 minutes.

The obtained unsaturated polyester plate was colorless and transparent, had no cracks, did not peel from the glass plate, and did not peel from the glass plate even after being left continuously at 150° C. for 48 hours. The volumetric shrinkage rate was 2.4%.

Example 3 To 95 parts of the unsaturated polyester (A) obtained in Example 1, 5 parts of 1,6-hexanethiol dimethacrylate (manufactured by Mitsubishi Rayon Co., Ltd.) and 0.0 parts of dimethylbenzyl ketal were added.
3 parts were added to obtain a composition (A-3) of the present invention.

Thereafter, it was treated and cured in the same manner as in Example 1.

The obtained unsaturated polyester plate was colorless and transparent, had no cracks, did not peel from the glass plate, and did not peel from the glass plate even after being left continuously at 150° C. for 48 hours. The volume shrinkage rate was 3.0%.

Comparative Example 1 0.3 mol of maleic anhydride, 0.7 mol of adipine #&, and 1.05 mol of diethylene glycol were reacted with stirring at 200° C. in a nitrogen gas stream to obtain an unsaturated polyester with an acid value of 21.

To 100 parts of this unsaturated polyester, 33 parts of diethylene glycol dimethacrylate was added, and further 0.05 part of cobalt octenoate (metal content 6% by weight, manufactured by Dainippon Ink and Chemicals) and methyl ethyl ketone peroxide (manufactured by NOF Corporation) were added. ) and the resulting resin composition was treated and cured in the same manner as in Example 2.

The obtained unsaturated polyester plate was transparent with a slight yellow color, but it was partially peeled off from the glass plate and heated at 150°C/4.
After being left for 8 hours, approximately 50% peeling occurred. The volume shrinkage rate was 6.0%.

Example 4 3.6-Nindomethylene-1. 2. 3. 1 mol of 6-tetrahydrophthalic acid, glycidyl methacrylate (
To a mixture of 2.3 mol (manufactured by NOF Corporation) and 0.01 mol of triethylbenzylammonium chloride, 1% by weight of hydroquinone and 1% by weight based on the total amount of the mixture were added.
00% by weight of ethylene dichloride was charged into a flask equipped with a Liebig water condenser and reacted at 80°C to obtain an unsaturated polyester with an acid value of 4.5. This unsaturated polyester was depressurized at 40° C. and 20 fiHg to remove ethylene dichloride to obtain an unsaturated polyester (B) with an acid value of 8.7.

To 100 parts of this unsaturated polyester (B), 3 parts of cumene hydroperoxide (manufactured by NOF Corporation) was added to obtain a composition (B-1) of the present invention.

Thereafter, it was treated and cured in the same manner as in Example 2.

The obtained unsaturated polyester plate was pale yellow and transparent, had no cracks, did not peel from the glass plate, and did not peel from the glass plate even after being left continuously at 150° C. for 48 hours. The volumetric shrinkage rate was 1.8%.

Example 5 To 95 parts of the unsaturated polyester (B) obtained in Example 4, 5 parts of methyl methacrylate and 3 parts of hendiine ethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were added to prepare the composition of the present invention (
B-2) was obtained.

Thereafter, it was treated and cured in the same manner as in Example 1.

Claims (1)

[Claims] 1,3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride or 3,6-endomethylene-1
An unsaturated polyester composition comprising an unsaturated polyester modified with , 2,3,6-tetrahydrophthalic acid, an organic peroxide and/or a photopolymerization initiator. 2. The unsaturated polyester composition according to claim 1, which contains a crosslinkable monomer.