JPS60228527A - Ultraviolet-curable resin composition - Google Patents

Abstract

PURPOSE:The titled resin composition which difficultly undergoes thermal embrittlement (caused by heating at about 150 deg.C for several hours), prepared by mixing polyethylene terephthalate resin with a cation-polymerizable compound and a photopolymerization initiator at a predetermined ratio. CONSTITUTION:An ultraviolet-curable resin composition is obtained by mixing a resin based on polyethylene terephthalate (which may be used in conjunction with about 30wt% or below polybutylene terephthalate resin or polycarbonate resin) with 50wt% or below, based on said resin, cation-polymerizable compound having a plurality of oxirane rings (e.g., bisphenol A epoxy resin) and 0.1- 10wt%, based on said polymerizable compound, photopolymerizable initiator (i.e., a compound which can release a Lewis acid catalyst upon irradiation with ultraviolet rays, e.g., aromatic diazonium salt).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention provides a molded product of polyethylene terephthalate resin that is not subjected to cooling stretching treatment at a relatively low temperature, for example, /! ; It relates to an ultraviolet curable resin composition that has improved the phenomenon of embrittlement caused by heating at 0° C. for several hours.

[Prior art]

It is used extensively in the insulation and textile industries.

The crystal structure of all these materials is oriented and regulated by cooling stretching treatment and heat setting treatment, making them strong and flexible.
It is well known that at a temperature of about 200° C., the crystal structure does not easily change and flexibility is maintained.

However, if this PET is integrally molded with a constituent material such as a metal, subsequent cooling and stretching treatment is impossible, and as a result, PET is severely thermally embrittled and cannot be put to practical use.

In view of these points, the inventors of the present invention integrally molded this useful PET, which has been used for many years, with other constituent materials such as metal, and without performing a cooling stretching process (even though it would not cause thermal embrittlement). We succeeded in obtaining a PFiT-based resin composition that does not.

PET molded products are highly flexible even without cooling stretching treatment by adjusting the cooling rate, etc., but even at 1410°C, which is relatively low compared to the processing temperature, the crystal structure changes in a few hours. become brittle. Therefore, in order to prevent changes in the crystal structure, we considered mixing various functional resins and performing crosslinking with various crosslinking agents, but crosslinking may progress partially or completely depending on the PET manufacturing temperature. However, the molded product itself could not be stably obtained due to gelation during processing.

However, the present inventors have found that only compositions containing a certain type of functional resin and a Lewis acid-releasing photopolymerizer capable of initiating polymerization of the functional resin are stable to heat, and are stable at a temperature of PET extrusion processing. However, they have finally discovered that it not only hardly decomposes and can be freely molded, but also retains its UV polymerization function after the process.

Thus, by mixing an epoxy resin with a resin whose main component is PET and adding a Lewis acid-releasing photopolymerization agent,
We have succeeded in obtaining an excellent, innovative resin composition that can be freely molded and does not cause heat embrittlement only by subsequent ultraviolet treatment.

[Summary of the invention]

The present invention relates to a cationically polymerizable compound comprising a resin whose main component is polyethylene terephthalate resin and an epoxy resin which has one or more oxirane rings in one molecule.
A photopolymerization initiator for the cationically polymerizable compound that releases the Lewis acid catalyst by ultraviolet irradiation is added to the polyethylene terephthalate resin in an amount of SO weight percent or less relative to the polyethylene terephthalate resin, and a photopolymerization initiator for the cationically polymerizable compound that releases the Lewis acid catalyst by ultraviolet irradiation.
0% by weight of an ultraviolet curable resin composition.

The PET used in the present invention is preferably commercially available, such as a film or fiber grade, or a bottle grade with an increased degree of polymerization using the same phase polymerization method.
If this is the case, then special request for isophthalic acid! ;t-/91/
Polyarylate resin known to be compatible with PET according to No. 3, and also JP-A-5T-iJtqo.
It is also possible to use a polycarbonate resin which is known to be compatible according to Publication No. b and substituted with PET in an amount of 30% by weight or less.

The cationically polymerizable compound used in the present invention is one or more cationically polymerizable compounds whose main component is an epoxy resin having λ or more oxirane rings in one molecule, and this epoxy resin includes bisphenol A type epoxy resin. ,
Preferred are novolac type epoxy resins, alicyclic epoxy resins, and the like.

Such bisphenol A type epoxy resins include 161 and Yuba Epicoat gλg, Epicoat T3 Hiro, Epicoat 136, Ehi:s-door θθl, Epicoat) 100
Hiroshi, Epicor) toot (manufactured by Shell Chemical Co., Ltd., product name), DWR33/, DER,? J co, D E R6
4/, DERtbda, DE) (667 (manufactured by Dow Chemical Company, Western product name), Araldite) J A O, Aral 1 DaitokogO, Araldite 1aO7/, Araldite) 40t'f, Araldite 1,097 ( Above, (manufactured by Ciba Geigy, trade name), etc., and these are used in combination or in combination. 1. Also, as the novolac type epoxy resin.

For example, Epicort 13, Epicor) 2.141 (manufactured by Shell Chemical Co., Ltd., trade name), Araldite F, PN
I/3g, 7 Araldite EPNtt, 3t, Araldite ECN/Co3S, Araldite ECN/Core 3, Araldite ECN/210. acyldite rvcN/2q
q (manufactured by Ciba Geigy, product name), l') EN%
j/, DENp, ytr (manufactured by Dow Chemical Company,
(trade name), and these can be used alone or in combination.

Further, as the alicyclic epoxy resin, for example, Araldite CY/RIS, Araldite CY/7, Araldite CY/lde, Araldite CY/lu, Araldite) CY/? λ (manufactured by Ciba Geigy, product name),
Examples include ERL-Li, 22/, RRL-Hirokodeta, and ERL-Kuko 3hiro (hereinafter, manufactured by Union Carbide, trade name), and these may be used alone or in combination.

Other butadiene-based epoxy resins can also be used, and mixtures of the various epoxy resins mentioned above can also be used.

A l-functional epoxy diluent may be used in the cationically polymerizable compound within a range that does not deteriorate the curing properties. Examples of such l-functional epoxy diluent include Fe=
Examples include glycidyl ether and t-butyl glycidyl ether.

Furthermore, it is also possible to use a cationically polymerizable vinyl compound mixed with the epoxy resin, and such cationically polymerizable vinyl compounds include styrene, allylbenzene, triallyl isocyanate, triallylcyanate, vinyl ether, N - vinyl carbazole,
Examples include N-vinylpyrrolidone.

The photopolymerization initiator used in the present invention to release a Lewis acid catalyst that initiates polymerization of a cationic polymerizable compound by ultraviolet irradiation includes aromatic diazonium salts, aromatic halonium salts, and group VIa or group Va elements. Examples include photosensitive aromatic onium salts.

Such an aromatic diazonium salt has the general formula (■): (
In the formula, R/, RJ are a hydrogen atom, an alkyl group or an alkoxy group, RJ is a hydrogen atom, an aromatic group or an aromatic group connected by an amide group or a sulfur atom, M is a metal or metalloid, and Q is a halogen atom and a = (
b - c ) holds true, parentheses C is an integer between λ and 7 and equal to the valence of M, and b represents an integer greater than C and less than or equal to l), for example, .

Further, the aromatic halonium salt has the general formula (■): (
In the formula, R# is a monovalent aromatic organic group, Rr is a covalent aromatic organic group, X is a halogen atom such as I, Br, OL, M is a metal or metalloid, and Q is a halogen atom. , d is 0 or co, e is □ or l, and (d+e) is co or equal to the valence of X, and g represents an integer greater than h and equal to or less than l), For example, etc.

Further, as a photosensitive aromatic onium salt of a group Via element or a group Va element, the general formula aII) : [(R,)
;(R,), (n,)ky]; (MQm)-(In”
) ([0) (wherein, R4 is a heptavalent aromatic organic group, R7
is a monovalent aliphatic organic group selected from the group consisting of an alkyl group, a cycloalkyl group, and a substituted alkyl group, and Rt is a heterocyclic group or a fused ring structure selected from an aliphatic organic group and an aromatic organic group. polyvalent organic group, Y is B, 8e
, Group Via elements of Te or N, P, As.

Group Va element selected from sb and B1, M is a metal or metalloid and Q is a halogen atom, 1 is O
j is an integer of θ~ko, k is an integer of O-1, and (1+, 1+k) is an integer of Yn), and n is an integer of λ~ and is the valence of M. equivalently, m represents an integer greater than n and less than or equal to t),
Examples of onium salts of Group Vla elements include, and examples of onium salts of Group Va elements:
For example, etc.

The amount of the Lewis acid free type polymerization initiator added to the cationically polymerizable compound is 0.00% of the cationically polymerizable compound.
/ -70% by weight preferably 7-3 weight axe, 0
When it is less than 7% by weight, the crosslinking reaction rate by ultraviolet # tends to be slow and the treatment time tends to be too long, and when it exceeds io% by weight, the price of the resin composition increases due to the high catalyst cost.

The composition of the present invention can be used for constituent materials integrated with metal or the like by molding such as injection, extrusion, or pressing, such as corrosion-resistant metal materials, electronic circuit boards, and insulated wires. Further, for the ultraviolet cross-linking treatment after mold processing, irradiation with a light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, or an electron beam irradiation is used.

[Embodiments of the invention]

Next, the composition of the present invention will be explained in detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 717 parts by weight of PET (Belene) was freeze-pulverized to produce bulk (
block), Epicoat (bisphenol A type epoxy resin), ? 03ii parts of triphenylsulfonius hexafluoroandemonate and 03 parts by weight of triphenylsulfonius hexafluoroandemonate were mixed and kneaded in a kneader at 2KO℃ for io minutes, then cooled and pelletized, and the pellets were heated in a barrel λSO℃,
Hera)" 2 I O'CW Futsubaki, -su-T, / T
') = Yu,. Oshide Sakaki. Add cypress to the opper and use a T-shaped die to make it OJjm thick! The composition was extrusion coated onto a copper strip of Ovm to a thickness of goμ to obtain a single-sided monolithically planted copper strip.

The 3 diameter/1σ bending characteristics of this molded product and the
A steel ball with a diameter of Afi was placed, a load of /hour was applied on it, 100 AC was applied between the steel ball and the copper strip, and it was heated in a constant temperature bath for about
The softening points measured from K when the temperature was increased at a rate of .degree. C./min are shown in Table 1.

Example: Pellets obtained in the same manner as in Example 1 were placed in a barrel 2jθ.
℃, the mixture was placed in the hopper of an extruder with L/D = t held at the head IO"Q, and extruded onto a 10 m diameter copper wire using a crosshead to a thickness of θμ to obtain an insulated wire. JIB
The results of measuring the winding flexibility and softening point according to C3003 are shown in Table 1.

Example J 10 parts by weight of PET pellets were freeze-pulverized into a bulk form, mixed with 20 parts by weight of Epicoat tSX (novolac type resin) and ajlf part of diphenyliodonium hexafluorophosphinium, and mixed with a kneader. The pellets were kneaded at 0°C for 70 minutes, then cooled and pelletized.
The mixture was put into the hopper of an extruder with L/D = 2 g held at 70° C., and extruded into a 70-diameter copper wire to a thickness of 0 μm to obtain an insulated wire. Table 1 shows the results of measuring the winding flexibility and softening point according to JIS C300J.

Example: 70 parts by weight of Hiro PET pellets was added to p-chlorophenol 3
? 7 parts by weight, 20 parts by weight of Epicote g cot,
and io parts by weight of Epicote IS2 are dissolved and dispersed,
Next, io parts by weight of a 30% propylene carbonate solution of triphenylsulfonium hexafluoroantimonate was additionally dissolved to obtain a transparent homogeneous solution.

The solvent was sufficiently removed from this solution at 100°C under reduced pressure.
Melt at J ff O ℃ in a melting tank with a structure that allows nitrogen gas to be discharged from the lower hole under pressure, connect the discharge hole to a crosshead with the same mechanism as that for ordinary wire coating, and use dies and nipples. 4Lo thick on 10m diameter copper wire.
Coated with μ. At this time, the temperature of the crosshead is 290℃
Met. Note that this coating method is generally called a hot melt coating method.

The results of measuring the winding flexibility and softening point of the obtained insulation 1tIfji according to JIS C300JK are shown in Table 1.

Comparative example / PET pellets were put into the hopper of an extruder with L/D = 2g held at 0°C and head at 9Q°C,
Using a T-shaped die, a copper strip with a width of 30 μm was extrusion coated onto a copper strip having a width of 0.0 mm and a width of 30 μm, to obtain a single-sided single-sided copper strip. Table 1 shows the bending properties and softening points obtained by the same method as in Example 1.

Comparative example CoPET 17) Pellets were heated in a barrel at 30°C, head 21
/, Q
It was extruded onto a fi copper wire to a thickness of go μ to obtain an insulated wire.

Table 1 shows the measurement results of winding flexibility and softening point according to JIS C3003.

Comparative Example 3 10 parts by weight of PIT pellets were dissolved in 33 parts by weight of p-chlorophenol, and glycidyl ether of bisphenol A (viscosity 1.20 to lsO poise/coj'C, epoxy f #t t 41 to 19 Gramdlc FC-os / / (
20 parts by weight (trade name, manufactured by Dainippon Ink Chemical Industries, Ltd.) were dissolved and dispersed, and then 02 parts by weight of Co-, cordiethoxyacetophenone as a photopolymerization initiator was further dissolved to obtain a transparent homogeneous solution.

The solvent was removed from this solution in the same manner and under the same conditions as in Example D, and an attempt was made to coat a copper wire with a diameter of 10Vx using the so-called hot melt coating method. However, the molten composition gelled and no insulated wire was obtained.

〔Effect of the invention〕

As is clear from the experimental results shown in Table 1, the molded products made only of PET shown in Comparative Examples 7 to 7 suffer from severe thermal embrittlement and are not suitable for practical use. In addition, the use of acrylate crosslinking agent was in Comparative Example H.
As shown in c, gelation occurs during the molding process and a molded product cannot be obtained. On the other hand, in Examples/~Hiro of the present invention, gelation did not occur during the molding process, and the molded products obtained had a low softening point as the epoxy resin acted as a plasticizer when not irradiated with ultraviolet rays. , thermal embrittlement phenomenon is also observed, but by UV irradiation treatment, the softening point is also improved, and -0
It can be seen that the embrittlement caused by thermal deterioration at 0°C is almost completely improved.

Furthermore, molded products using the composition according to the present invention that have been subjected to ultraviolet irradiation treatment have excellent mechanical strength, electrical insulation properties, solvent resistance, etc., and are therefore extremely useful compositions. confirmed.

Procedural Amendment (Spontaneous) 1932, 1936, 1932, 1932, 1932, 1932, 1932, 1932, 1933, Patent Application No. TSRZI 2, Title of Invention: Ultraviolet Curing Layer Resin Composition 3, Person Making Amendment Related Patent applicant address: 2-2-3-4 Marunouchi, Chiyoda-ku, Tokyo; agent address: 4th floor, Marunouchi Building, 2-4-1, Marunouchi 2-4-1, Chiyoda-ku, Tokyo; column for detailed description of the invention in the specification - 6-・′-
--2'-- Contents of amendment (1) The description is amended as follows.

Continuing from page 1 ■Int, C1,' Identification symbol Office organization O Inventor Shoji Hirabayashi Moichi Tsukaguchi; Inside the Science Institute

Claims (1)

[Scope of Claims] (1) A resin whose main component is polyethylene terephthalate resin and/or one or more cationic polymerizable compounds whose main component is an epoxy resin having λ or more oxirane rings in the molecule of the polyethylene terephthalate resin. 3 for resin
0 weight percent or less, and further contains a photopolymerization initiator for the cationic polymerizable compound that releases the Lewis acid catalyst upon irradiation with ultraviolet rays, at θ1 to 70 weight percent based on the cationic polymerizable compound. Composition. (co) The photopolymerization initiator is one or more selected from the group consisting of aromatic diazonium salts, aromatic halonium salts, and photosensitive aromatic onium salts of Group VIa or Group Va elements. Claim 1 which is a mixture
The ultraviolet curable resin composition described in 1. (3) The ultraviolet curable resin composition according to claim 1, wherein 30 weight percent or less of the polyethylene terephthalate resin is replaced with a polybutylene terephthalate resin, a polyarylate resin, or a polycarbonate resin.