JPH01247455A - Unsaturated polyester resin composition for cathode ray tube processing - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an unsaturated polyester resin composition for cathode ray tube processing.

(Prior Art) Since the inside of a cathode ray tube is maintained at a high vacuum, there is a risk of crushing or implosion due to atmospheric pressure, and therefore cathode ray tubes require explosion-proof treatment.

Among these explosion-proof treatments, the method with the highest front safety is the explosion-proof treatment method in which the front glass is bonded to the cathode ray tube face plate using an explosion-proof resin composition. That is, the first
As shown in the figure, on the face plate part 2 of the cathode ray Wl,
Front glass 3 with the same curvature and almost the same size as this
All of them are separated by a minute distance and surrounded and held by tape 4, during which time RK is held.

Explosion-proof cathode ray/f is filled with explosion-proof treatment resin composition 5.
Chiru by the method of forming I6.

Conventionally, epoxy resin compositions and unsaturated polyester resin compositions have been used as resin compositions for this explosion-proof treatment, but each has advantages and disadvantages.

At present, a resin composition for treating cathode ray tubes that satisfies both properties and workability has not been obtained.

For example, epoxy resin compositions have a strong adhesive force and are convenient for bonding the front glass to the face plate, but due to their nature, they have a coloring property (kana), so they cannot be used in colors such as those used in color cathode ray tubes. This is not desirable in cases where importance is placed on Furthermore, for products such as color cathode ray tubes, which have high added value, recycling is also a top priority.
In the case of epoxy resin, the adhesive strength is strong, so it is easy to damage the faceplate part when removing the front glass.

It is nearly impossible to remove this glass.

Furthermore, since epoxy resin compositions have a higher viscosity than unsaturated polyester resin compositions, they have the disadvantage that bubbles that are mixed in during mixing of a curing agent or injection of resin are difficult to remove. Moreover, the viscosity of epoxy resin increases rapidly immediately after mixing with the curing agent, so the pot life for injection is very short, and in order to perform the work smoothly, a separate mixing device or injection device is required for 1%, making the work easier. is also very poor.・On the other hand, in unsaturated polyester resin compositions.

The viscosity is generally relatively low, a few poise, and it is difficult to mix curing agents,
It is easy to inject resin between the cathode ray tube face plate and the front glass, and its viscosity is low.

Although it has advantages such as good bubble removal during mixing and injection, if the ratio of several curing agents used to the unsaturated polyester resin composition changes from the specified conditions, curing distortion may occur locally during curing. This hardening distortion becomes a lens effect when the cathode ray tube is operated.

It appears as stripes or bright spots on the screen.

These striped patterns and bright spots impair the value of the product, so careful attention must be paid to the mixing ratio of the curing agent.

Moreover, since curing distortion occurs due to rapid heating or uneven temperature in the curing furnace, sufficient temperature control must be carried out.

Although unsaturated polyester resin compositions have many problems in table production as mentioned above, they have low viscosity and good bubble removal and 9
Has little coloring and excellent transparency.

Furthermore, although its adhesive strength is weaker than that of epoxy resins, it is sufficient for practical use, and it has many advantages, such as being relatively easy to recover.

Improvements over the conventional techniques that take advantage of the advantages of such unsaturated polyester resin compositions are disclosed in Japanese Patent Application Laid-open No. 148263/1982 and 148264/1982. The methods shown in these documents prevent the occurrence of bright spots and striped patterns due to curing distortion by adjusting the polymerizable monomer that crosslinks the unsaturated polyester.

(Problems to be Solved by the Invention) The present invention aims to maintain the advantages of unsaturated polyester resin compositions, such as low viscosity, transparency, and adhesive strength, while eliminating the generation of bright spots and striped patterns. The object of the present invention is to provide an unsaturated polyester resin composition for wire tube treatment.

(Means for Solving the Problems) The present invention provides an acid component containing an unsaturated polybasic acid and/or its acid anhydride, and optionally another saturated polybasic acid and/or its acid anhydride, and an alcohol. Cross-linking an unsaturated polyester with a blending amount of 5 to 20% by weight of an unsaturated polybasic acid and/or its acid anhydride obtained by reacting propylene glycol or polypropylene glycol as a component with the refractive index of the unsaturated polyester. The difference between the theoretical refractive index of the chain is related to ±chill tree J Feng.

Among the acid components used in the present invention, unsaturated polybasic acids and/or their acid anhydrides include maleic acid, maleic anhydride, fumaric acid, and itaconic acid.

Examples include citraconic acid and itaconic anhydride. Two or more of these may be used in combination.

Examples of the saturated polybasic acid and/or its acid anhydride that may be used as necessary include phthalic acid and phthalic anhydride.

Isophthalic acid, terephthalic acid, trimellitic acid.

Trimellitic anhydride, succinic acid, azelaic acid.

Adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, anthracene-maleic anhydride adduct, rosin-maleic anhydride adduct, het acid, het anhydride acid, tetrachlorophthalic acid, tetradichlorophthalic anhydride. Tetrabromophthalic acid.

Examples include tetrabromo phthalic anhydride. these are.

Two or more types may be used in combination.

As the polypropylene glycol, polymers of propylene glycol are used, such as dipropylene glycol and tripropylene glycol.

Polypropylene glycol (Sannix PP-400
, PP-750, PP-950, PP-1000, PP
-1200,PP-2000,PL)-3000,PP
-4000 (manufactured by Sanyo Chemical Co., Ltd.)), and two or more of these may be used in combination.

The production method for producing unsaturated polyester by reacting the above acid component and alcohol component is mainly carried out by promoting a condensation reaction, and low molecules such as water produced when the two components react are removed from the system. Proceed by letting go.

The reactor for this reaction is selected from materials such as glass and stainless steel that are inert to acid components, and includes a stirring device and a fractionator to prevent distillation of the alcohol component due to azeotropy between water and alcohol component. 9. It is preferable to use a reaction apparatus equipped with a heating device for raising the temperature of the reaction system, a temperature control circuit for this heating device, and a blowing device for nitrogen gas or the like.

The reaction condition is preferably carried out at a temperature of 150° C. or higher at which the reaction rate is sufficiently high. In order to prevent coloring due to oxidation reactions at high temperatures, the temperature range is more preferably from 160°C to 210°C.

Furthermore, in order to prevent side reactions due to oxidation at high temperatures, it is preferable to carry out the synthesis while passing an inert gas such as 1gi element or carbon dioxide.

The reaction proceeds by heating a system in which an acid component and an alcohol component are mixed, and removing low-molecular compounds such as condensed water from the system. , and is carried out by vacuum distillation. Further, if the low molecular weight compound to be distilled has a high boiling point, a high vacuum is required.

Furthermore, in order to promote the distillation of low-molecular compounds such as condensed water, a solvent such as toluene or xylene can be added to the system as an azeotropic component to perform natural distillation.

The progress of the reaction can generally be known from K, such as measuring the amount of distillate produced by the reaction, quantifying the terminal functional group, and measuring the viscosity of the reaction system.

The unsaturated polyester used in the present invention is:

The amount of unsaturated polybasic acid and/or its acid anhydride is 5 to 5.
It is assumed to be 20% by weight.

If this compounding amount is 5% by weight without grooves, sufficient cross-linking may not occur during resin curing, curing may be extremely slow, the injected resin may leak, or the molding time may take a long time. It turns out. On the other hand, if this blending amount exceeds 20 weights, the crosslinking density of the cured resin product will become high, and therefore,
This increases the shrinkage of the resin and causes failure in peeling it off from the front glass and the face plate of the ttach tube.

The unsaturated polyester thus obtained is dissolved in a certain acrylic polymerizable monomer to form an unsaturated polyester resin.

As the acrylic polymerizable monomer used in the present invention,
Acrylic acid, allyl acrylate, benzyl acrylate,
Butyl acrylate, ethyl acrylate, methyl acrylate, propyl acrylate.

Hydroxyethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, allyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, dodecyl methacrylate, )! Octyl taacrylate, pentyl methacrylate, trimethylolpropane tri(meth)acrylate (indicates methacrylate or acrylate; the same applies hereinafter), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,
triprolene glycol di(meth)acrylate, brobylene glycol di(meth)acrylate), 1,6-hexanethiol di(meth)acrylate), 1.4-butanediol di(meth)acrylate, dicyclopentadiene (meth)acrylate, ethylene glycol mono(
Acrylic acid, methacrylic acid, or derivatives thereof, such as meth)acrylate, diethylene glycol mono(meth)acrylate, and neobentylglycol di(meth)acrylate, are used, and these polymerizable monomers may be used alone or in combination of two or more. Can be used in combination.

These polymerizable monomers are selected depending on the type of unsaturated polyester, and the reason for selection is the difference in refractive index from the unsaturated polyester.

In addition, the difference in theoretical refractive index between unsaturated polyester and crosslinked chains (products when acrylic polymerizable monomers are crosslinked) is ±
Must be within 0.05.

If the difference in refractive index exceeds ±0.05, bright spots or striped patterns are likely to occur due to uneven curing when the unsaturated polyester and the polymerizable monomer are cured.

Here, the theoretical refractive index of the crosslinked chain is determined by the following formula from the refractive index and weight fraction when the acrylic polymerizable monomer used is homopolymerized.

Bridging chain refractive index n=1n, XW, +! 12XW2+
, , -1-n, XWll where n1~. : Refractive index of the homopolymer of the acrylic polymerizable monomer used (this value is determined by measurement or literature) W1~. : Weight fraction of the acrylic polymerizable monomer used The reaction of the unsaturated acid in the unsaturated polyester that occurs in the crosslinking chain when the unsaturated polyester resin is cured is ignored.

The unsaturated polyester resin composition of the present invention has H, IK
Hydroquinone, pyrocatechol, 2,6-di-
A polymerization inhibitor such as tert-butyl para-cresol may also be added.

The unsaturated polyester resin composition of the present invention contains metal soaps such as cobalt naphthenate, cobalt octenoate, copper naphthenate, manganese naphthenate, calcium naphthenate, potassium octenoate, and zinc naphthenate, either alone or in combination. is also used. The amount of metal soap added is
There is no particular limit, but it is better to have as little as possible in relation to the coloration of the cured product, and cobalt naphthenate (metal content 6%, Dainippon Ink Chemical Industry Co., Ltd.) is 0% compared to unsaturated polyester and polymerizable monomer. A range of .01 to 0.15% by weight is preferred.

Further, the unsaturated polyester resin composition according to the present invention is
Curing accelerators such as dimethylbenzylammonium chloride, ethyl acetoacetate, acetylacetone, dimethylaniline, N-ethyl metatoluidine triethanolamine, and photopolymerization initiators such as diphenyl disulfide, benzoin, benzoin methyl ether, benzoin ethyl ether, dimethylbenzyl ketal, etc. It can also be photocured using .

The unsaturated polyester resin composition of the present invention is as follows.

It may also contain dyes, plasticizers, ultraviolet absorbers, etc., if necessary.

The unsaturated polyester resin composition for cathode ray tube processing prepared as described above is injected between the face plate and front glass of cathode ray tubes such as cathode ray tubes for televisions and display tubes for computers, and then hardened.

(Example) The present invention will be explained below with reference to Examples. The ``chi'' indicates weight %.

Example 3I equipped with a stirrer, condenser, nitrogen gas introduction pipe, and thermometer! 213 g of propylene glycol (trade name of Recall) fumaric acid 4069 was placed in a four-bottle flask, and the temperature was raised to 150°C over 1.5 hours using a mantle heater while slowly flowing nitrogen gas. 4 more
The temperature was raised to 200° C. over time and kept at that temperature. Unsaturated polyester All with an acid value of 23 in about 8 hours,'
h.

The temperature was further lowered to 100° C., 0.3 g of hydroquinone was added as a polymerization inhibitor, and the mixture was poured onto a stainless steel vat and cooled to room temperature. The unsaturated acid content of this unsaturated polyester A was 14.9.

This unsaturated polyester resin was dissolved in an acrylic polymerizable monomer according to the formulation shown in Table 1 to obtain an unsaturated polyester resin composition. Cobalt octenoate (gold IA-containing
0.05% of Nippon Ink Chemical Industries, Ltd.) and 1% of Permec N (55% methyl ethyl ketone peroxide manufactured by Nippon Oil & Fats) were added.

On the other hand, thickness 3aaX 250anaX 250al [1
1 on transparent flat glass, thickness 3m x 250m + uX
Leaving the periphery of the silicon plate at 250 [+1111 mm], the inside was cut out with a razor to a size of 240 mm x 240 mm, and a silicone plate with a slit injection port was placed in one place around the remaining periphery as a spacer. A transparent child glass plate with a thickness of 3 mtn x 250 mm x 250 marks was placed on top of this spacer, and the glass plates were fastened with a stopper to obtain a casting jig. The above unsaturated polyester resin composition was injected through the slit inlet of the spacer between the casting jigs.

The resin was then left to stand at 110° C. for 1 hour to harden the resin to obtain an unsaturated polyester resin casting plate.

Table 1 shows the properties of the casting plate thus obtained. In addition, a casting plate was prepared in the same way, and half of the casting plate was covered with polyethylene foam for partial heating.

As before, leave it in an electric dryer at 60°C for 60 minutes,
The resin was further left to stand at 110°C for 1 hour, and the resin was cured to obtain an unsaturated polyester resin casting plate. I counted the number of.

(Effects of the Invention) The unsaturated polyester resin composition for cathode ray tube processing according to the present invention can eliminate the striped pattern caused by curing distortion that conventionally occurs in cathode ray tubes due to uneven heating, etc., and can improve the yield and quality of cathode ray tubes. We can expect improvement.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of a cathode ray tube. Explanation of symbols 1...Cathode ray tube 2...Face plate portion 3...Front glass 4...Tape 5...
resin composition

Claims (1)

[Claims] 1. Reacting propylene glycol or polypropylene glycol as an alcohol component with an acid component containing an unsaturated polybasic acid and/or its acid anhydride and, if necessary, other saturated polybasic acid and/or its acid anhydride. The blending amount of the obtained unsaturated polybasic acid and/or its acid anhydride is 5 to 5.
The difference between the refractive index of the unsaturated polyester and the theoretical refractive index of the crosslinked chain is ±0.20% by weight of the unsaturated polyester.
An unsaturated polyester resin composition for cathode ray tube processing, which is obtained by dissolving an acrylic polymerizable monomer selected to have a concentration of 0.05 or less.