JPS6217051A - Glass tube collecting agent - Google Patents

Abstract

PURPOSE:To obtain the titled collecting agent having excellent thermal stability and inodorousness in melting and further having excellent solubility in solvents by hydrogenating the cyclopentadiene polymer as the agent for collecting glass tubes which are combined with semiconductors in the circuit element for electrical and electronic equipment. CONSTITUTION:The titled agent consists of the hydrogenation product of a cyclopentadiene polymer and/or a cyclopentadiene compd.-vinyl-substituted aromatic hydrocarbon copolymer. The collecting agent is the hydrogenated polymer and/or the hydrogenated copolymer obtained by hydrogenating the polymer or the copolymer with the use of a catalyst such as Pd and Ni or their mixture. When the collecting agent is used, a bundle of plural glass tubes is dipped in the melt of the collecting agent, pulled up, cut in prescribed length and washed with a solvent such as toluene to dissolve and remove the collecting agent and the glass tube having desired length is obtained.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a glass tube binding agent, and more specifically, a glass tube binding agent that has excellent thermal stability and odor when melted, and excellent solubility in solvents. Regarding drugs.

[Prior art] Some circuit elements such as diodes used in electronic and electrical equipment are made of silicon (Si) or germanium (Ge).
) and other semiconductors with an outer diameter of 0.5 to 1.5 mm and a length of 1
There is a combination with an ultra-thin glass tube of about 3 hm.

Such glass tubes are manufactured by cutting glass tubes with an outer diameter of about 0.5 to 10 mm into desired lengths, but at this time, the following method is applied to improve manufacturing efficiency. It is common to do so. That is, after a plurality of glass tubes are immersed in a molten glass tube binding agent, they are taken out, cooled, and fixed by the glass tube binding agent, and the bundle is cut into a predetermined length. Afterwards,
By dissolving and removing the sizing agent with a suitable solvent, a glass tube of the desired size is obtained.

[Problems to be Solved by the Invention] As such a glass tube sizing agent, a mixture of pine tar and paraffin has conventionally been used. Although this sizing agent has the ability to fix glass tubes, since pine tar is a natural product, the supply of raw materials is unstable, and when the sizing agent is removed, the solubility of the sizing agent in the solvent is low. There is a problem.

Therefore, as an alternative glass tube convergence agent.

Cyclopentadiene polymer or cyclobentadiene-
One made of styrene copolymer has been proposed. However, this sizing agent does not have good thermal stability when melted and also generates a bad odor when melted, so there is still room for improvement.The present invention solves these conventional problems. The purpose of the present invention is to provide a glass tube binding agent which not only has a high ability to fix glass tubes, but also has excellent thermal stability and odorlessness during melting, as well as excellent solubility in solvents.

[Means for Solving the Problems] As a result of extensive research in order to achieve the above object, the inventors discovered that, as will be described later, a product obtained by hydrogenating a conventional glass tube sizing agent was The present invention was completed based on the discovery that it satisfies all the properties required for a glass tube sizing agent.

That is, the glass tube sizing agent of the present invention is characterized by comprising a hydrogenated product of a cyclopentadiene copolymer and/or a cyclopentadiene compound-vinyl-substituted aromatic hydrocarbon copolymer.

[Specific explanation] The glass tube sizing agent of the present invention is as described above.

It is a hydrogenated product of a cyclopentadiene-based polymer, a hydrogenated product of a cyclopentadiene-based compound-vinyl-substituted aromatic hydrocarbon copolymer, or a mixture of these two.

First, the cyclopentadiene polymers include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, dimers, trimers, and codimers thereof. Examples include polymers of such compounds, and among them, cyclopentadiene polymers and dicyclopentadiene polymers are preferred. Further, as the cyclopentadiene compound, a mixed fraction obtained by thermal decomposition of petroleum may be used.The cyclopentadiene may be used as it is during the preparation, but dicyclopentadiene may be used as it is. This can be decomposed during the copolymerization reaction to form cyclopentadiene.

On the other hand, the cyclopentadiene-based compound-vinyl-substituted aromatic hydrocarbon copolymer is a copolymer of the above-listed cyclopentadiene-based compound and a vinyl-substituted aromatic hydrocarbon. The vinyl-substituted aromatic hydrocarbon is not particularly limited, and includes, for example, styrene, α-methylstyrene, vinyltoluene, etc. Among these, styrene is preferred.

The composition ratio of these two copolymerization components is not particularly limited, but for example, the cyclopentadiene compound is 95 to 5% by weight, more preferably 80 to 50% by weight, and the vinyl substituted aromatic hydrocarbon is 95 to 5% by weight. 5-85% by weight, even 20
It is preferable to set the usage amount of each of them so that the total amount is 100% by weight at 50% by weight.

These polymers and copolymers are produced as follows.

That is, in the zero reaction in which a cyclopentadiene compound alone or a cyclopentadiene compound and a vinyl-substituted aromatic hydrocarbon are charged in a predetermined ratio and a polymerization reaction is carried out, a solvent may be used as necessary. good. The solvent to be used is not particularly limited, but suitable examples include aromatic, naphthenic, or paraffinic hydrocarbons. The amount of the solvent used is 0 to 500 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the mixture of the cyclopendiene compound or cyclopentadiene compound and the vinyl-substituted aromatic hydrocarbon. is set to The reaction temperature is preferably set at 250 to 300°C, more preferably 260 to 280°C, and the reaction time is preferably set at 0.5 to 10 hours, preferably 1 to 5 hours.

Next, the thus obtained polymer or copolymer is hydrogenated to obtain a hydrogenated polymer or copolymer. In this reaction, examples of catalysts used include Pd, Ni, and Pt-based catalysts.

The amount of catalyst used is not particularly limited, but based on 100 parts by weight of the above-mentioned polymer or copolymer,
The amount is set at 1 to 10 parts by weight, preferably 3 to 7 parts by weight. Moreover, a solvent can be used as necessary during the reaction. Specific examples of the solvent include naphthenic or paraffinic hydrocarbons, ethers, ketones, and esters. The amount of such a solvent used is not particularly limited, but is 0 to 50 parts by weight based on 100 parts by weight of the polymer or copolymer.
The amount may be set to 0 parts by weight, preferably 50 to 150 parts by weight.

In this hydrogenation reaction, the hydrogen pressure is 1O~100kg
/ ad, more preferably set to 30 to 50 kg/ad, and the reaction temperature is 100 to 250 kg/ad.
℃, even 120~200℃, reaction time 0.5~
It is preferable to set each time to 10 hours, more preferably 1 to 8 hours.

The properties of the polymer or copolymer thus obtained are approximately as follows. That is, molecular weight by vapor pressure measurement method: 500 to 1500, bromine number = θ to lO
g/100g, softening point = 50 to 200°C, oxidation: 1 or less, hue (Gardner chromaticity): 1 or less. In addition, the styrene skeleton content in the copolymer is 5 to 60% by weight.
, and more preferably about 20 to 40% by weight.

The glass tube sizing agent of the present invention is a hydrogenated product of the above-mentioned cyclopentadiene-based polymer or a hydrogenated product of a cyclopentadiene-based compound-vinyl-substituted aromatic hydrocarbon copolymer, or.

It is made by mixing both in an arbitrary ratio.

This glass tube sizing agent is used, for example, in the following manner.

That is, first, the glass tube sizing agent is melted in a container. The melting temperature needs to be higher than the softening point of the glass tube sizing agent, and is usually 130 to 180°C. Next, a bundle of a plurality of glass tubes is immersed in the melt of the glass tube sizing agent for, for example, 1 to 30 minutes, and after the glass tubes are pulled up, the sizing agent is cooled and solidified. Thereafter, this convergent body is cut into a predetermined length using, for example, a diamond cutter, and then washed with a solvent to dissolve and remove the glass tube convergence agent, thereby obtaining a glass tube of a desired length.

The solvent used at this time may be any solvent that can dissolve the glass tube sizing agent described above, such as toluene,
perchlorethylene, xylene, trichlorethylene,
Chloroform, dichloroethane, dichloroethane, or a mixed solution thereof is preferred.

[Example] Example 1 (1) Preparation of glass tube sizing agent 300 g of cyclopentadiene and 300 liters of pheasant 9 fu! ; Pour into L autoclave and carry out polymerization reaction at 280°C for 1.5 hours to obtain 272 g of polymer.
I got it. This material had a softening point of 72°C and a bromine number of 85. Next, 200 g of this polymer was mixed with cyclohexane 2
Using 10 g of Pd-silica alumina catalyst containing 0.5% by weight of Pd as a catalyst,
Hydrogenation was carried out for 2 hours at a hydrogen pressure of 50 kg/cm 2 and 210'O. As a result, 199 g of a hydrogenated polymer, ie, a glass tube sizing agent, was obtained. This material had a softening point of 98°C and a bromination level of 0.5.

(2) Production of glass tubes The glass tube sizing agent obtained above was melted at 150°C, and the outside diameter lam and length 300 m were added to the melt.
The glass tubes 42 of each layer were bundled and immersed for 10 minutes so that the longitudinal direction of the glass tubes was perpendicular to the liquid level. After being pulled out, the tubes were cooled and solidified in air.

As a result, the above glass tubes are converged to form 8II11×
A glass tube converging body of 7+w+a x 30hm was obtained. Next, Idemitsu Kosan AL-38 was used as cutting oil.
This converging body was cut into 21 widths using a diamond cutter on a plane perpendicular to the longitudinal direction of the glass tube.

After that, the obtained convergence body piece was first diluted with 20% of toluene.
The glass tube sizing agent was preliminarily washed with a mixed solvent consisting of 0- and perchlorethylene 200- to dissolve and remove it, and then the main cleaning was performed with a neutral detergent to completely remove the sizing agent. A glass short tube of m was obtained.

In the manufacturing process of short glass tubes using such a glass tube sizing agent, the following evaluation tests were conducted to evaluate whether the glass tube sizing agent satisfies the required characteristics. .

(A) The viscosity of the heat-stable glass tube sizing agent was measured after being melted at 150°C in air for 20 hours, and the viscosity increase rate (%) with respect to the initial value was measured.

(B) The presence or absence of odor was investigated when the odorless glass tube sizing agent was melted at 150°C.

No odor...O1 odor...
...×(C) Non-flammability (flash point) The flash point ("O) of the glass tube sizing agent was measured in accordance with JIS K 22fi5.

(D) Convergence (Fixing ability) After converging the glass tubes with a glass tube convergence agent, the fixity of the glass tubes was evaluated when the convergence body was cut with a diamond cutter.

No separation of glass tubes ・・・・・・O Some separation of glass tubes ・×(E) Non-shrinkage Glass tube sizing agent melted at 150°C 150mmX
The sample was poured into a 30 am x 2 mm mold and cooled to room temperature, and was visually inspected for cracks.

No cracks・・・・・・・・・0 Cracks・・・・・・・・・× (F) Stability against cutting oil The weight of the glass tube sizing agent and cutting oil They were mixed at a ratio of 1:1 and shaken for 1 minute, and their meltability was examined 24 hours later.

Insoluble ・・・・・・・・・〇Partially insoluble・・・・・・・・・Δ Dissolved ・・・・・・・・・× (G) Solubility of glass in solvent w Convergence agent and toluene/park It was mixed with a mixed solvent of rollethylene (weight ratio: 1), shaken for 1 minute, and examined for solubility 24 hours later.

Dissolution ・・・・・・・・・O Insoluble or poorly soluble...× The above results are summarized in the table.

Example 2 200 g of cyclopentadiene, 200 g of styrene, and 200 g of xylene were charged into an autoclave having an internal volume of 1 cm, and a polymerization reaction was carried out at 260° C. for 1.5 hours to obtain 353 g of a polymer. The softening point of this product was 72°C, the bromine number was 58, and the styrene skeleton content was 50% by weight. Next, 200 g of this polymer was dissolved in 200 g of cyclohexane, and 0.5% by weight of P was added as a catalyst.
Using 10 g of Pd-silica/alumina catalyst containing d, hydrogenation was carried out at a hydrogen pressure of 30 kg/cm and at 200° C. for 5 hours. As a result, 199 g of a hydrogenated polymer, ie, a glass tube sizing agent, was obtained. The softening point of this product was 102°C, the bromination was 4.5, and the styrene skeleton content was 33% by weight.

Using this glass tube sizing agent, short glass tubes were manufactured in the same manner as in Example 1 above, and the same evaluation tests were conducted, and the results are shown in the table.

Comparative Example 1 A short glass tube was produced in the same manner as in Example 1, except that a mixture of pine resin and paraffin wax at a weight ratio of 97:3 was used as the glass tube sizing agent. In addition, a similar evaluation test was conducted and the results are shown in the table.

Comparative Example 2 A short glass tube was produced in the same manner as in Example 1 above, except that the polymer before hydrogenation obtained in Example 1 above was used as a glass tube sizing agent, and the same method was used. An evaluation test was conducted and the results are shown in the table.

Comparative Example 3 A short glass tube was produced in the same manner as in Example 1 above, except that the polymer before hydrogenation obtained in Example 2 above was used as a glass tube sizing agent, and the same method was used. An evaluation test was conducted and the results are shown in the table.

[Effects of the Invention] As is clear from the above explanation, it goes without saying that the glass tube binding agent of the present invention is excellent in binding and fixing properties of glass tubes, and particularly has excellent thermal stability during melting, odorlessness, It is far superior to conventional glass tube sizing agents in terms of non-flammability and solubility in solvents, so its industrial value is extremely high, especially in the field of manufacturing electronic and electrical circuit elements. be.

Claims (1)

[Claims] A glass tube binding agent comprising a hydrogenated product of a cyclopentadiene polymer and/or a cyclopentadiene compound-vinyl-substituted aromatic hydrocarbon copolymer.