JPH03190919A - Epoxy resin - Google Patents

Abstract

PURPOSE:To obtain a crystalline epoxy resin capable of providing an adhesive epoxy resin formed article suitable for adhesive, sealing agent, etc., by blending the resin with a filler and curing agent and forming the blend into a sheet and punching the sheet, by reacting m-aminophenol with terephthalic acid diglycidyl ester, etc., at a specific ratio. CONSTITUTION:(A) m-Aminophenol is reacted with (B) terephthalic acid diglycidyl ester or hydroquinone diglycidyl ether at a ratio of epoxy resin of the composition B to active hydrogen of the composition A which is 1.5-15 (equivalent ratio) to provide the crystalline epoxy resin. When 35-100 pts.wt. of the epoxy resin is blended with 0-75 pts.wt. epoxy resin (e.g. bisphenol A type epoxy resin) being a solid at ambient temperature, 0-100 pts.wt. filler (e.g. mica) and 0.1-20 pts.wt. curing agent (e.g. diethylene triamine) and the blend is formed into a sheet in uncured state and punched, an adhesive formed article capable of bonding and sealing by bringing it into contact with a material to be bonded or sealed and heating, melting and curing it can be obtained.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention utilizes a crystalline epoxy resin used for adhesives, sealants, etc., an epoxy resin composition, a method for producing a molded product thereof, and a molded product thereof. related to adhesion and sealing methods.

(Prior art) Recently, there has been an increasing need for bonding and sealing small, minute parts such as electronic parts, but it is difficult to apply only to such relatively small areas where it is necessary. In the case of adhesives, extrusion and insufficient filling are likely to occur. In addition, thermosetting adhesives are often required for electronic parts, and in this case, there are many difficulties in workability and handling due to viscosity changes and delta formation due to the progress of the curing reaction. For this reason, such applications require pre-molded adhesives of the same type, but in the case of thermosetting adhesives of the same type, conventionally powdered thermosetting resins, compounding materials, additives, A manufacturing method has been adopted in which powders such as a hardening agent are triblended and the powdered mixture is processed into a molded body using a tablet machine. However, since the molded product obtained by this method is brittle and easily chipped, there are significant restrictions on the shape and size that can be manufactured, and it may not be suitable for the needs for bonding small and fine parts as described above. In addition, the same type of adhesive manufactured by conventional methods is brittle and is easily damaged by vibrations during transportation, etc., and generates powder between the time it is manufactured and the time it is used for bonding parts, etc. This powder may cause problems such as staining the adhered material. Furthermore, since the L: same type adhesive manufactured using the conventional method is made by compacting powdered adhesive, the state after melt bonding contains many air bubbles inside, and it cannot be said to be a highly reliable adhesive. .

Next, in the case of conventional epoxy resin adhesives of the same type, in order to prevent insufficient filling of the adhered object during melt curing, the molecular weight of the epoxy resin is lowered, a plasticizer is added, or a crystalline epoxy resin [e.g. Manufactured by Shell Co., Ltd., YX-400
0, etc.) to lower the viscosity during melt-hardening. However, according to these methods, the molded bodies block each other at room temperature, resulting in many difficulties in workability and handling.

Furthermore, when a crystalline epoxy is blended, there are drawbacks such as a decrease in curing reactivity.

(Problems to be Solved by the Invention) The object of the present invention is to provide a crystalline epoxy resin which has an extremely low viscosity when melted and hardened, and which has excellent filling properties for adhered objects, and which has a small and fine shape and is breakable. An adhesive epoxy resin composition that is difficult to bond, hardly generates powder due to friction, etc., and is in a substantially uncured state and does not contain air bubbles inside after melt bonding, a method for producing a molded product thereof, and use of the molded product. An object of the present invention is to provide a bonding, sealing, and sealing method.

(Means for Solving the Problems) The present invention combines (,), -ami7phenol and (1)) terephthalic acid diglycidyl ester or hydroquinone diglycidyl ether with an active hydrogen (A) and an epoxy group (
A crystalline epoxy resin obtained by addition reaction so that the equivalent ratio of B) becomes (B)/(A)=i, 5 to 15, an epoxy resin composition, a method for producing a molded product thereof, and a molded product thereof. This relates to the adhesive and sealing method used.

The present invention will be specifically explained below.

In the present invention, the equivalent ratio of the active hydrogen (A) of (a) II+-ami/7er/-l to the epoxy group (B) of (()) terephthalic acid diglycidyl ester or hydroquinone diglycidyl ether is (B) / (A) = 1.5
An addition reaction is performed between the two in an amount relationship of ~15. In this case, if (B)/(A) is less than 1.5, the crystallinity of the resulting epoxy resin may be lost or the gel may form as the reaction progresses. It may become Also, if the size is larger than (B)/(A) 5, the crystallization speed of the resulting epoxy resin will be very fast, causing many difficulties in workability and handling, and it will be extremely difficult to form into a film or sheet. Become.

With this amount relationship, terephthalic acid diglycidyl ester or hydroquinone diglycidyl ether was heated at 120°C.
Above 150℃, preferably 130"CI:J, Upper 1
After sufficiently melting at 35"C or less, "1-amino7
Add the alcohol and stir for 5 to 30 minutes, preferably 5 to 10 minutes, to ensure thorough and uniform melt mixing. Immediately thereafter, a yellowish-white crystalline epoxy resin is obtained by rapid cooling. This crystalline epoxy resin has a slow crystallization rate, so it has excellent workability and handling.
It can be molded into a film or a sticker by itself without requiring reinforcement. It also has a 7-ether hydroxyl group in its molecule, which reacts with and crosslinks with epoxy groups, making it highly reactive.
The resulting cured product is characterized by a high crosslinking density.

A crystalline epoxy resin having such characteristics has not been previously available.

100 parts by weight of an epoxy resin of the same type at room temperature containing at least 35 parts by weight of the crystalline epoxy resin thus obtained contains 0 to 100 parts by weight, preferably 0 to 75 parts by weight of a filler. An epoxy resin composition is obtained by mixing and kneading up to 20 parts by weight. It is also possible to add known formulations if necessary. Since this epoxy resin composition has crystallinity, it melts rapidly at a temperature higher than its melting point, and is characterized by excellent filling properties into objects to be adhered.

The epoxy resin composition obtained in this way is formed into a film or sheet with a thickness of 10 mn from the 0,0] + cocoon in a substantially uncured state, and then the film or sheet is punched to form an adhesive epoxy resin composition. A resin molded body can be produced, and the molded body is heated and melted at a temperature lower than the melting point of the molded body in a state in which the molded body is in contact with an object to be adhered or an object to be fixed, and further Adhesion by curing, 14
can be stopped.

1 as the same type of epoxy resin at room temperature used in the present invention.
Type A epoxy t'rj JJ)?
Epicoat +001, manufactured by C Yuka Shell Epoxy Co., Ltd.
1002°100:1. +004.1005.100
7.1010.1100L, etc.], brominated bisphenol A type epoxy resin [manufactured by Yuka Shell Epoxy Co., Ltd., Eviny] 5050. 5051.

5051 H, etc.], 0 to 100 parts by weight cresol novolak type epoxy resin [manufactured by Sumitomo Chemical Co., Ltd., ESCII-
220F.

F'': 5CN-220H, ESCN-220T- (H, etc.), brominated 7-borac type epoxy resin [Nippon Kayaku Co., Ltd.]
BRF N-S, etc.], 7 ether/borac type epoxy resins [ESPN-180, etc., manufactured by 1 Yukagaku Co., Ltd.], and epoxy resins modified from these.

These epoxy resins can be used together, and even if they are liquid epoxy resins at room temperature or B-stage epoxy resins, these epoxy resins can be used together at room temperature (25°C). Although they can be used as long as they are of the same type, it is preferable to adjust the melting point of this mixture to 50-120°C. If the melting point is less than 50°C, the molded products will be in a semi-isomorphic state at room temperature, causing a problem that the molded products will block each other at room temperature. On the other hand, when the temperature exceeds 120°C, the elution 1 temperature becomes high.
Energy loss is large.

Fillers used in the present invention include undefeated fillers such as mica, silica, lath fibers, glass flakes, glass powder, titanium oxide, zinc oxide, carbon fiber, talc, and calcium carbonate, aramid fibers, nylon fibers, etc. For example, there are fillers that can be used as fillers. Further, flame retardants, reinforcing materials, lubricants, dispersants, surfactants, pigments, dyes, coupling agents, etc. may be added as necessary. Flame retardant materials include antimony trioxide, aluminum hydroxide, red phosphorus, and halogen compounds.
As reinforcing materials, polyamide resin, polyester cypress ■, polycarbonate cedar 1, polyurethane a
T fat, silicone resin, thermoplastic resin such as 7e7xy resin, or elastomer, lubricant, dispersant, surfactant such as wax, zinc stearate, silicone oil, pigment and dye such as carbon black, Examples of the coupling agent include red iron, titanium white, cyanine blue, etc., and titanium coupling agent. As a means for melt-mixing, a kneading extruder, a heating stirring tank, a Nigu, a Banbury mixer,
Examples include rolls and the like.

Examples of the curing agent include amine-based curing agents, acid anhydride-based curing agents, 7-el resin-based curing agents, catalyst-based curing agents, etc., and there is no particular limitation as long as the curing agent can undergo a curing reaction with the epoxy resin. However, a curing agent of the same type is preferably used at room temperature.

Specific examples of amines include noethylenetriamine, 1
-lyethylenetetramine, bis(hexamethylene)l diamine, trimethylhexamethylene monodiamine, menthensoamine, isophorone diamine, metaxylylene diamine, 3,9-bis(3-ami7propyl)-2,4,8-tetraspiro [5,5:l undecane, metaphenylenediamine, noami7phenylmethane, diaminodiphenylsulfone, 4.4゛-methylenebis(2-chloroaniline) and the agct of this with epoxy resin, etc., as specific examples of acid anhydrides. As an example, anhydrous 7
Talic acid, trimetic anhydride, pyromellitic anhydride, benzo-7e/nthe-lacarboxylic anhydride, maleic anhydride, tetrahydro-7-talic anhydride, hexahydro-7-talic anhydride,
Specific examples of 7-ethyls include methylnadic anhydride, methylsic-U-hexenetetracarboxylic anhydride, tetrachloro-7-talic anhydride, tetrabromo-7-talic anhydride, etc.
Phenol, 0-cresol 7volac, 7er7-7
Examples include borax, 7-araralkyl, and the like. Examples of the catalytic curing agent include benzyldimethylamine, 2,4.6 TrisC dimethylaminomethyl)Fe7
tertiary amines such as -ol, viverline, pyrinone, and picoline; imidazoles represented by 2-ethyl-4-methyl imiguzole;
, 4,0] undecene, BF, etc., dicyandiamide, amine imide, organic acid hydrazide, mixtures of these, salts, complexes, and the like. The amount of curing agent is usually 0.1 to 20 parts per 100 parts of epoxy resin in the case of catalyst type curing agent.
l+r, otherwise 0 in equivalent ratio to epoxy group
．． It is preferable to set it as the range of 5-2.

In the present invention, the epoxy resin composition is used in a substantially uncured state as a film or sheet (hereinafter simply referred to as a sheet).
In addition to extrusion molding using an extruder equipped with a sheet die and rolling the material into a sheet using calendar rolls, mold release groups can be formed by solution coating, hot melt coating, etc. using a coating machine. It is also possible to form a sheet on top of the material. Regardless of which method is used, the epoxy resin mixture can be impregnated into the base material or laminated to form a composite sheet by supplying an MIi fibrous base material such as a glass fiber nonwoven fabric or glass cloth as appropriate. is also possible. The sheet of the uncured epoxy resin mixture obtained in the above method is further processed using a punching press, etc. using a punching die, a Thomson blade die, a chisel die, etc. It is punched out using a punching machine to obtain an epoxy resin molded body having the desired shape.

Here, the term "substantially uncured state" means a state where crosslinking has partially progressed but has not been completed. If the thickness of the sheet is less than 0.0]m+n, it will not be affected by the impact during punching.

Moreover, even if punched through, the strength of the molded product is very low and handling is difficult. On the other hand, the thickness] O+n +n
If it exceeds this value, accurate punching becomes difficult. During punching, it is important to keep the sheet above the plus transition temperature and below the softening temperature >8. This is because the material strength of the epoxy resin mixture, which is formed into a sheet in a substantially uncured state, is not sufficient to withstand punching at temperatures below the glass transition temperature, and may stick to the cutting die at temperatures above its softening temperature. This is because it is not suitable for punching, as it is impossible to maintain the shape after punching. In addition, the punching machine used in the present invention is equipped with a device such as a heating plate or a constant temperature bath that controls the temperature of the epoxy resin mixture sheet to a temperature suitable for punching, which is higher than the glass transition temperature and lower than the softening temperature. It is preferable that Furthermore, when punching is performed using a punching die, the temperature of the punching die must also be controlled.

For example, when forming a sheet using an extruder, after the extruded sheet is cooled to below the softening temperature by a cooling drawer or the like, and before being cooled to below the glass transition temperature,
It is also possible to perform punching in succession with extrusion molding, and in this case there is no need to equip the punching machine with a sheet temperature control device.

By heating the adhesive epoxy resin molding obtained in this manner (hereinafter simply referred to as "molding") to a temperature higher than the melting point of the molding while in contact with an object to be adhered or an object to be sealed, The molded body melts and wets the object to be adhered or sealed, and after flowing to the required area, a curing reaction proceeds,
The adhesive or seal is cured.

There are shapes of molded bodies to improve adhesion or sealing properties to objects to be adhered or sealed, such as rod-shaped, flat plate-shaped, ring-shaped, frame-shaped, film-shaped, pellet-shaped, and strips. Examples include a shape in which a hole is formed, and a shape in which a hole is formed.

(Effects of the Invention) According to the method for producing an adhesive epoxy resin molded article of the present invention, it is possible to mold an adhesive thermosetting molded article with smaller and finer shapes and dimensions without cracking or chipping, and the number of adhesive molded articles has increased recently. It can fully meet the needs for adhesion and sealing of small and minute parts such as electronic parts, which are becoming increasingly popular. In addition, the molded product obtained by the method of the present invention has sufficient strength to be handled by automated equipment such as Parts Figu and Robots 1, so it has excellent effects on process automation and cost reduction. . In addition, the molded product obtained by the method of the present invention is resistant to handling and vibration during conveyance, so it does not break and generates less powder due to abrasion, so it is suitable for adherend parts. It is less likely to contaminate etc. Furthermore, according to the method of the present invention, it is possible to obtain a denser molded body, so that bubbles are not generated inside after melt bonding (or l'J11-), and stronger bonding is possible. .

On the other hand, according to the #adhesive Epoquine resin molded article of the present invention, it is possible to manage the quantity of the adhesive, the adhesive (=volume), the positioning (=shape) of the object to be adhered or the object to be sealed, and the robot 1, etc. Adaptation to automation (same type, high strength) is possible, and assembly by adhesion and sealing becomes extremely easy. In addition, since the main component is epoxy resin, it has excellent heat resistance, chemical resistance, solvent resistance, electrical properties, adhesion, adhesion, etc.

(Example) Examples and comparative examples will be described below.

Examples 1 to 4 and Comparative Example 1-4 Terephthalic acid noglycidyl ester [manufactured by Nagase Kasei Co., Ltd., Bunacol E] was added to a flask equipped with a stirrer and a thermometer.
X71.1. ．． WPE=149] 149. and stir thoroughly while keeping the flask at 13°C (1°C).When no residual isomorphic material is observed and the mixture is sufficiently melted,
t0 to 100 parts by weight of Ami 77 7-el are charged at once into a flask at the mixing ratio shown in Table 1. After continuing stirring for 10 minutes, the reactants in the flask were rapidly cooled.
A crystalline epoxy resin can be obtained.

Table 1 Example 5 and Comparative Example 5 The crystalline epoxy resin A 2 (obtained in Example 2) and the same type of epoxy resin at room temperature [Bisphenol A type epoxy resin manufactured by Jigyo Shell Co., Ltd. , Eviny) 1 (104), using silica as the filler, the second
They were blended at the blending ratio shown in the table and premixed using a Henschel mixer to obtain a powdery mixture. Next, this mixture was thoroughly melt-mixed at 170-180'C using a heated roll, the temperature was lowered to 120-130'C, and 2
-Add 2 parts by weight of ethyl-4-methylimitasole,
After mixing for a minute, 0.5
It was pressed into a sheet having a thickness of 11,116 mm. The obtained sheet-like composition was punched into a disk shape with a diameter of 10 mm, and this molded body was used for terminal sealing of electronic components, resulting in a melamine resin electronic component body and a silver-plated copper terminal. It was confirmed that the adhesive was firmly attached. The curing conditions at this time were 100°C and 130 minutes.

In Table 2, regarding the punching workability of the 0.5m+n thick sheet for each sample, those that are easy are marked with a "○", and those that are possible are marked with a "○".
Those that are impossible are marked with an "X". Regarding the filling properties of the adherend during melting, those that completely flowed and filled were marked with an "O" mark, and the others were marked with an "X" mark.

As is clear from Table 2, samples 1-3.5-7.9-
11 is within the scope of the present invention, and 0.5In In
It is confirmed that the punching processability of the thick sheet and the filling property into the adherend during melting are good. Sample 4°8.12 contained a large amount of filler and had a high viscosity during melt sealing, resulting in poor filling properties to the adherend. Samples 13 to 16 are 0.5+n11
The 1-thick sheet itself was extremely brittle and difficult to punch out, making it unusable.

The wooden seal is a comparative example.

Table 2 Examples 6 to 9 and Comparative Examples 6 to 9 In the same manner as in Example 1, hydroquinone nobricidyl erucyl [manufactured by Nagase Kasei Co., Ltd., Bunacol EX203]
．． WPE=112'l 112. using Il+
A crystalline epoxy resin was obtained by reacting with Ami77E7-el at the blending ratio shown in Table 3.

Table 3 9 Example 10 and Comparative Example 10 Using the crystalline epoxy A7 (obtained in Example 7) and using the same method as in Example 5, the same type of epoxy resin [Yuka Shell Co., Ltd.] was prepared at room temperature. 10043, a type A epoxy resin manufactured by Bis7el, manufactured by Ebiny), was blended with silica as a filler at the proportions shown in Table 4, and punched molded products were obtained and evaluated in the same way.

Table 4 0 As is clear from Table 4, Samples 17-19.21-2
3, 25 to 27 are within the scope of the present invention, and 0.5
It is confirmed that the punching processability of the Ill In thick sheet and the filling property into the adherend during melting are good. Sample 20 can be easily punched, and samples 24 and 28 can also be punched, but both contain a large amount of filler and have a high viscosity at the time of melting, making it difficult to fill the adherend. The sex was inferior.

(hereinafter “2)” Sender: Toyo Tire & Rubber Industries Co., Ltd.

Claims (4)

[Claims] (1) (a) m-aminophenol and (b) terephthalic acid diglycidyl ester or hydroquinone diglycidyl ether with an equivalent ratio of active hydrogen (A) to epoxy group (B) of (B)/(A) = 1 A crystalline epoxy resin obtained by addition reaction so that the ratio becomes .5 to 15. (2) Epoxy resin 1 of the same type at room temperature (25°C) containing at least 35 parts by weight of the crystalline epoxy resin according to claim 1.
00 parts by weight, filler 0 to 100 parts by weight, curing agent 0.1 to
An epoxy resin composition containing 20 parts by weight. (3) Adhesive epoxy resin molding characterized by forming the epoxy resin composition of claim 2 into a film or sheet having a thickness of 0.01 mm to 10 mm in a substantially uncured state, and then punching out the film or sheet. How the body is manufactured. (4) The adhesive epoxy resin molded body obtained by the manufacturing method according to claim 3 is heated at a temperature equal to or higher than the melting point of the molded body while it is in contact with an object to be adhered or sealed to melt it. An adhesion and sealing method characterized by curing and curing.